KR20240021961A - Polyester/polyester elastomeric composition - Google Patents

Abstract

(a) one or more rigid polyesters; (b) one or more polyester elastomers; (c) one or more primary antioxidants; (d) one or more secondary antioxidants; and (e) one or more chain extending additives, wherein the polyester composition has a melting enthalpy of less than or equal to 3 cal/gm. Methods for making the polyester composition, and articles comprising the polyester composition are also provided.

Description

Polyester/polyester elastomeric composition

The present invention generally relates to a polyester composition comprising at least one rigid polyester and at least one polyester elastomer, at least one primary antioxidant, at least one secondary antioxidant, and at least one chain extender, as well as the polyester composition comprising: It relates to articles made from ester compositions. Methods for making the polyester compositions as well as methods for making articles comprising the polyester compositions are provided.

Useful compositions comprising rigid polyester and copolyester elastomers having improved thermal stability and improved physical and processing properties are disclosed. Thermoplastic polyesters are typically considered rigid thermoplastics with high tensile strength and modulus values. Thermoplastic polyester elastomers are typically considered inherently flexible materials with lower tensile strength and modulus values. In certain applications, it is useful to use materials that have physical properties between rigid and elastomeric polyesters. It is also useful for certain applications and processing techniques, such as powder coatings with improved color, processing and thermal stability properties. The present inventors have discovered that various rigid polyester and polyester elastomer compositions containing thermal stabilizers produce useful materials with improved initial color, improved thermal stability, and physical properties.

In one embodiment of the invention, (a) one or more rigid polyesters; (b) one or more polyester elastomers; (c) one or more primary antioxidants; (d) one or more secondary antioxidants; and (e) one or more chain extending additives, wherein the polyester composition has a melting enthalpy of less than or equal to 3 cal/gm.

In another embodiment of the invention, to produce a polyester composition, a mixture of (a) one or more rigid polyesters; (b) one or more polyester elastomers; (c) one or more primary antioxidants; (d) one or more secondary antioxidants; and (e) one or more chain extending additives, wherein the polyester composition has a melting enthalpy of less than or equal to 3 cal/gm.

In another embodiment of the invention, in an extrusion zone to produce a polyester composition, there is provided a mixture of (a) one or more rigid polyesters; (b) one or more polyester elastomers; (c) one or more primary antioxidants; (d) one or more secondary antioxidants; and (e) one or more chain extending additives, wherein the polyester composition has a melting enthalpy of less than or equal to 3 cal/gm.

In another embodiment of the invention, the method comprises: (a) polymerizing at least one dicarboxylic acid and at least one diol to produce a rigid polyester having a T _g greater than 60°C; (b) polymerizing at least one dicarboxylic acid, at least one diol, and at least one polyol to produce a polyester elastomer having a T _g of less than 50° C.; (c) contacting the rigid polyester with the polyester elastomer and one or more chain extending additives to produce a polyester composition, wherein the polyester composition has a weight of 3 cal. has an enthalpy of melting of less than or equal to /gm; the polymerization in steps (a) and/or (b) is carried out in the presence of one or more primary antioxidants; The polymerization in steps (1) and/or (2) is carried out in the presence of one or more secondary antioxidants.

In another embodiment of the invention, (a) polymerizing one or more dicarboxylic acids and one or more diols in the presence of (1) one or more primary antioxidants and (2) one or more secondary antioxidants at a temperature above 60°C. producing a rigid polyester having a T _g of; (b) polymerizing at least one dicarboxylic acid, at least one diol and at least one polyol to produce a polyester elastomer having a T _g of less than 0°C; and (c) contacting the rigid polyester with the polyester elastomer and one or more chain extending additives to produce a polyester composition, wherein the polyester composition has 3 It has a melting enthalpy of less than cal/gm.

In another embodiment of the invention, the method comprises: (a) polymerizing at least one dicarboxylic acid and at least one diol to produce a rigid polyester having a T _g greater than 60°C; (b) polymerizing one or more dicarboxylic acids, one or more diols, and one or more polyols in the presence of (1) one or more primary antioxidants and (2) one or more secondary antioxidants to obtain a T _g of less than 0°C. producing a polyester elastomer having; and (c) contacting the rigid polyester with the polyester elastomer and one or more chain extending additives to produce a polyester composition, wherein the polyester composition has 3 It has a melting enthalpy of less than cal/gm.

In another embodiment of the invention, an article is provided comprising the polyester composition, wherein the polyester composition comprises: (a) one or more rigid polyesters; (b) one or more polyester elastomers; (c) one or more primary antioxidants; (d) one or more secondary antioxidants; and (e) one or more chain extending additives, wherein the composition has a melting enthalpy of less than or equal to 3 cal/gm.

In another embodiment of the present invention, a method of making a polyester-coated article is provided comprising coating the article with a polyester composition to produce a polyester coated article, wherein the polyester composition comprises: (a ) one or more rigid polyesters; (b) one or more polyester elastomers; (c) one or more primary antioxidants; (d) one or more secondary antioxidants; and (e) one or more chain extending additives, wherein the composition has a melting enthalpy of less than or equal to 3 cal/gm.

In another embodiment of the invention, a method of making a molded article is provided comprising the following steps:

(a) placing a polyester composition into a mold having a mold surface, wherein the polyester composition comprises: (1) one or more rigid polyesters; (2) one or more polyester elastomers; (3) one or more primary antioxidants; (4) one or more secondary antioxidants; and (5) one or more chain extending additives, wherein the composition has an enthalpy of melting of less than or equal to 3 cal/gm;

(b) heating the polyester composition until melted;

(c) dispersing the molten polyester composition to cover the mold surface;

(d) solidifying the molten polyester to form a solid molded article; and

(e) removing the molded article from the mold.

The invention may be more readily understood by reference to the following detailed description of specific embodiments and working examples of the invention. In accordance with the object(s) of the invention, certain embodiments of the invention are described in the foregoing Summary of the Invention and are further described below. Additionally, other embodiments of the invention are described herein.

Unless otherwise indicated, all numbers referring to amounts of ingredients, properties, such as molecular weight, reaction conditions, etc., used in the specification and claims herein are to be understood as being modified in all instances by the term “about.” Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired properties sought to be obtained by the invention. At the very least, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Additionally, ranges recited herein and in the claims are intended to specifically include the entire range and not just the endpoint(s). For example, a range referred to as 0 to 10 includes all integers between 0 and 10 (e.g., 1, 2, 3, 4, etc.), all decimal numbers between 0 and 10 (e.g., 1.5, 2.3, 4.57, 6.1113, etc.) etc.) and endpoints 0 and 10. Additionally, ranges relating to chemical substituents, such as “C ₁ to C ₅ hydrocarbons”, are intended to specifically include and disclose C ₁ and C ₅ hydrocarbons as well as C ₂ , C ₃ and C ₄ hydrocarbons.

Notwithstanding the fact that the numerical ranges and parameters disclosing the broad scope herein are approximations, the numerical values disclosing in specific embodiments are reported as accurately as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in its respective test measurement.

In the specification and claims, the singular forms “a,” “an,” and “the” include plural referents, unless the context clearly dictates otherwise. Reference to a composition or process containing or comprising “one” ingredient or “one” step is intended to include the other ingredients or other steps, respectively, in addition to those named.

The term "comprising" or "including" is synonymous with the term "comprising" and means that at least the named compound, element, particle or method step, etc. is present in the composition or article or method, but other compounds, substances, Even if particles, method steps, etc. have the same function as those named, the presence of other such compounds, catalysts, materials, particles, method steps, etc. is not excluded unless explicitly excluded in the claims.

The term “polyester” herein is synonymous with the term “resin” and is intended to mean a polymer prepared by polycondensation of one or more specific diacid components, a diol component, and, optionally, a polyol component.

The term "moiety" herein in relation to the polymers of the invention means any organic structure incorporated into the polymer through polycondensation or ring-opening reactions involving the corresponding monomers. Additionally, those skilled in the art will understand that the moieties associated within the various polyesters of the present invention may be derived from the parent monomeric compound itself or any derivative of the parent compound. For example, dicarboxylic acid moieties mentioned for the polymers of the present invention may be derived from dicarboxylic acid monomers or related acid halides, esters, salts, anhydrides, or mixtures thereof. Accordingly, the term "dicarboxylic acid" herein refers to dicarboxylic acids and any derivatives of dicarboxylic acids useful in polycondensation processes with diols to prepare curable aliphatic polyesters, such as their related acid halides, esters, It is intended to include semi-esters, salts, semi-salts, anhydrides, mixed anhydrides, or mixtures thereof.

The term “branching agent” refers to an alcohol or acid molecule having three or more functional groups. Examples of alcohol branching agents include glycerin, trimethylol propane, and pentaerythritol. Trimellitic anhydride is an example of an acid-based branching agent.

The term “polyol” herein refers to polymeric diols, such as polytetramethylene ether glycol (PTMG), polyethylene glycol, polypropylene glycol, etc. In some embodiments of the invention, the polyol has an absolute molecular weight of about 600 g/mol to about 5000 g/mol.

It should also be understood that reference to more than one method step does not exclude the presence of additional method steps before or after the combination of steps mentioned, or the presence of intermediate method steps between those explicitly identified steps. Moreover, the letters of method steps or ingredients are a convenient means for identifying separate activities or ingredients, and the letters cited may be arranged in any order, unless otherwise indicated.

The present invention provides a material comprising: (a) one or more rigid polyesters; (b) one or more polyester elastomers; (c) one or more primary antioxidants; (d) one or more secondary antioxidants; and (e) one or more chain extending additives, wherein the composition has a melting enthalpy of less than or equal to 3 cal/gm.

In other embodiments of the invention, the polyester composition has an enthalpy of melt of less than 3 cal/gm, less than 2.7 cal/gm, less than 2.5 cal/gm, less than 2.3 cal/gm, less than 2 cal/gm, 1.7 cal/gm. is less than, less than 1.5 cal/gm, less than 1.3 cal/gm, or less than 1 cal/gm. In other embodiments, the polyester composition has a melt enthalpy of 0.1 to 3 cal/gm, 0.3 to 3 cal/gm, 0.5 to 3 cal/gm, 0.7 to 3 cal/gm, 1 cal/gm, as measured by ASTM D3418. to 3 cal/gm, 1.2 to 3 cal/gm, 1.5 to 3 cal/gm, 2 to 3 cal/gm, 0.1 to 2.5 cal/gm, 0.3 to 2.5 cal/gm, 0.5 to 2.5 cal/gm, 0.7 to 2.5 cal/gm, 1 to 2.5 cal/gm, 1.5 to 2.5 cal/gm, 2 to 2.5 cal/gm, 0.1 to 2 cal/gm, 0.3 to 2 cal/gm, 0.5 to 2 cal/gm, 0.7 to 2 cal/gm, 1 to 2 cal/gm, 1.2 to 2 cal/gm, 1.5 to 2 cal/gm, 0.1 to 1.5 cal/gm, 0.3 to 1.5 cal/gm, 0.5 to 1.5 cal/gm, 0.7 to 1.5 cal /gm, 1 to 1.5 cal/gm, 0.1 to 1 cal/gm, 0.3 to 1 cal/gm, 0.5 to 1 cal/gm, 0.1 to 0.7 cal/gm, 0.3 to 0.7 cal/gm, or 0.1 to 0.5 cal /gm range.

In an embodiment of the invention, the polyester composition exhibits a blister size of at least 6, as determined by ASTM D714, after a 500 hour salt fog test in accordance with ASTM B117.

In another embodiment, the polyester composition exhibits a scribe rust value of at least 6, as determined by ASTM D1654.

In another embodiment of the invention, the polyester composition, when applied to a metal panel, has an impact resistance of at least 160 ft·lb, as measured by ASTM D2794. Other ranges of impact resistance are greater than 170 ft·lb, greater than 180 ft·lb, greater than 190 ft·lb, or greater than 200 ft·lb, as measured by ASTM D2794.

hard polyester

The rigid polyester may be any rigid polyester known in the art having a glass transition temperature (T _g ) greater than 60°C. Other rigid polyesters useful in the present invention include temperatures above 65°C, above 70°C, above 75°C, above 80°C, above 85°C, above 90°C, above 100°C, above 105°C, above 110°C, above 115°C, above 120°C. has a T _g greater than 125°C or greater than 125°C.

In another aspect of the invention, the T _g of the rigid polyester or copolyester useful in the invention may be, but is not limited to, one or more of the following ranges: 50 to 150° C.; 50 to 145°C, 50 to 140°C, 50 to 135°C, 50 to 130°C, 50 to 125°C, 50 to 120°C, 55 to 150°C; 55 to 145°C, 55 to 140°C, 55 to 135°C, 55 to 130°C, 55 to 125°C, 55 to 120°C, 60 to 150°C; 60 to 145°C, 60 to 140°C, 60 to 135°C, 60 to 130°C, 60 to 125°C, 60 to 120°C, 65 to 150°C; 60 to 145°C, 60 to 140°C, 60 to 135°C, 60 to 130°C, 60 to 125°C, 60 to 120°C, 65 to 150°C, 65 to 145°C, 65 to 140°C, 65 to 135°C, 65 to 130°C, 65 to 125°C, 65 to 120°C, 70 to 150°C; 70 to 145°C, 70 to 140°C, 70 to 135°C, 70 to 130°C, 70 to 125°C, 70 to 120°C, 75 to 150°C; 75 to 145°C, 75 to 140°C, 75 to 135°C, 75 to 130°C, 75 to 125°C, or 75 to 120°C.

The flexural modulus of the rigid polyester is greater than 1,000 Mpa, as measured by ASTM D790. In another embodiment, the flexural modulus of the rigid polyester is greater than 1,100 Mpa, greater than 1,200 Mpa, greater than 1,300 Mpa, greater than 1,400 Mpa, and greater than 1,500 Mpa, as measured by ASTM D790. In other embodiments of the invention, the flexural modulus of the rigid polyester is about 1,000 to about 2,600 Mpa, about 1,000 to about 2,500 Mpa, about 1,000 to about 2,000 Mpa, about 1,000 to about 1,500 Mpa, about 1,000 to about 1,400 Mpa. , about 1,000 to about 1,300 Mpa, about 1,100 to about 2,600 Mpa, about 1,100 to about 2,500 Mpa, about 1,100 to about 2,000 Mpa, about 1,100 to about 1,500 Mpa, about 1,100 to about 1,400 Mpa, about 1,100 to about 1,300 Mpa. 0 MPa, About 1,200 to about 2,600 Mpa, about 1,200 to about 2,500 Mpa, about 1,200 to about 2,000 Mpa, about 1,200 to about 1,500 Mpa, about 1,200 to about 1,400 Mpa, about 1,200 to about 1,300 Mpa, 1,300 to about 2,600 Mpa , about 1,300 to about 2,500 Mpa, from about 1,300 to about 2,000 Mpa, or from about 1,300 to about 1,500 Mpa.

Rigid polyesters useful in the present invention may include one or more diacid moieties and one or more glycol moieties. As used herein, the term “copolyester” is intended to include “polyester” and is comprised of one or more difunctional carboxylic acids and/or polyfunctional carboxylic acids and one or more difunctional hydroxyl compounds and/or polyfunctional hydroxyl compounds. It is understood to mean a synthetic polymer prepared by reaction. Typically, the difunctional carboxylic acid may be a dicarboxylic acid and the difunctional hydroxyl compound may be a dihydric alcohol, such as glycol. Additionally, the terms "diacid" or "dicarboxylic acid", which are interchangeable herein, include polyfunctional acids, such as branching agents. The term “glycol” herein includes, but is not limited to, diols, glycols, and/or multifunctional hydroxyl compounds. Alternatively, the difunctional carboxylic acid may be a hydroxy carboxylic acid, such as p-hydroxybenzoic acid, and the difunctional hydroxyl compound may be an aromatic nucleus with two hydroxyl substituents, such as hydroquinone.

The term “moiety” herein refers to any organic structure incorporated into the polymer through polycondensation and/or esterification reactions from the corresponding monomers.

As used herein, the term “repeating unit” refers to an organic structure in which a dicarboxylic acid residue and a diol residue are bonded through an ester group. Thus, for example, the dicarboxylic acid moiety may be a dicarboxylic acid monomer or a related acid halide, ester, half-ester, salt, half-salt, anhydride, mixed substance, etc. useful in reaction processes with diols to prepare polyesters. It may be derived from anhydride, or mixtures thereof.

The term "terephthalic acid" herein refers not only to terephthalic acid itself and its residues useful in reaction processes with diols for making polyesters, but also to any derivatives of terephthalic acid, such as its related acid halides, esters, half-esters, It is intended to include salts, semi-salts, anhydrides, mixed anhydrides, or mixtures thereof or residues thereof. The term “modifying aromatic diacid” refers to an aromatic dicarboxylic acid other than terephthalic acid. The term “modified glycol” refers to glycols other than 1,4-cyclohexanedimethanol. In one embodiment, terephthalic acid can be used as the starting material. In another embodiment, dimethyl terephthalate can be used as a starting material. In another embodiment, a mixture of terephthalic acid and dimethyl terephthalate can be used as starting material and/or intermediate material.

The polyesters and copolyesters of the present invention are readily prepared by methods well known in the art, as described, for example, in U.S. Pat. No. 2,012,267, the entirety of which is incorporated herein by reference. More particularly, the reaction to prepare the copolyester is generally carried out in the presence of a polycondensation catalyst (e.g., titanium tetrachloride, manganese diacetate, antimony oxide, dibutyl tin diacetate, zinc chloride, germanium, or combinations thereof). It is carried out at a temperature of about 150°C to about 300°C. The catalyst is generally used in an amount of 10 to 1000 ppm based on the total weight of reactants.

In one embodiment, the rigid polyester comprises dicarboxylic acid moieties and diol moieties; the dicarboxylic acid moiety is at least one selected from terephthalic acid and isothalic acid; The diol moiety is at least one selected from ethylene glycol and diethylene glycol. In another embodiment, the rigid polyester comprises cyclohexanedimethanol moieties, such as 1,4-cyclohexanedimethanol. In another embodiment, rigid polyesters useful in the present invention may contain ethylene glycol moieties.

Condensation polymers are also prone to hydrolysis if not pre-dried or if kept at elevated temperatures in humid air for long periods of time. A condensation polymer is any polymer in which monomers react during polycondensation to produce a polymer and by-products (such as water or methanol) are produced. The polymerization reaction is reversible, so condensation polymers are often pre-dried before processing.

The rigid polyesters used in the present invention can typically be prepared from dicarboxylic acids and diols that react in substantially equal proportions and are incorporated as their corresponding moieties into the rigid polyester polymer. Accordingly, the rigid polyester of the present invention contains substantially equal molar ratios of acid residues (100 mol%) and diol (and/or polyfunctional hydroxyl compound) residues (100 mol%), such that the total moles of repeat units are 100 mol%. mol%). Accordingly, mole percentages provided in the present invention may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeat units. For example, a polyester containing 70 mole percent terephthalic acid based on total acid residues means that the polyester contains 70 mole percent terephthalic acid residues out of 100 mole percent total acid residues. Therefore, for every 100 moles of acid residues there are 70 moles of terephthalic acid residues. In another example, a polyester containing 30 mole percent of 1,4-cyclohexanedimethanol residues, based on total diol residues, may be defined so that the polyester contains 30 mole percent of 1,4-cyclohexanedimethanol residues out of 100 mole percent total diol residues. , means that it contains a 4-cyclohexanedimethanol residue. Therefore, for every 100 moles of diol residues, there are 30 moles of 1,4-cyclohexanedimethanol residues.

In one embodiment, the rigid polyester or copolyester is a single diacid or a combination of diacids (e.g., cyclohexanedimethanol or ethylene glycol or other glycol with 2 to 20 carbon atoms) in combination with a modifying glycol (e.g., terephthalic acid or phthalic acid or other diacids having 8 to 20 carbon atoms).

In certain embodiments, the rigid polyester includes one or more diol moieties. In certain embodiments, the rigid polyester comprises one or more dicarboxylic acids or esters thereof and one or more diols, wherein the total acid residues present are 100 mole percent and the total diol residues present are 100 mole percent. In certain embodiments, the rigid polyester comprises a 1,4-cyclohexanedimethanol moiety.

In certain embodiments, terephthalic acid or an ester thereof, such as dimethyl terephthalate, or a mixture of terephthalic acid and an ester thereof, constitutes most or all of the dicarboxylic acid component used to form the rigid polyester useful in the present invention. . In certain embodiments, the terephthalic acid residues are present in the rigid polyester at a concentration of at least 70 mole %, such as at least 80 mole %, at least 90 mole %, at least 95 mole %, at least 99 mole %, or 100 mole %. It may constitute part or all of the dicarboxylic acid component used to form. In certain embodiments, rigid polyesters with high amounts of terephthalic acid may be used to produce higher impact strength properties. For the purposes of the present invention, the terms “terephthalic acid” and “dimethyl terephthalate” are used interchangeably herein. In one embodiment, dimethyl terephthalate is part or all of the dicarboxylic acid component used to prepare the polyester useful in the present invention. In all embodiments, in the range of 70 to 100 mole %, or 80 to 100 mole %, or 90 to 100 mole %, or 99 to 100 mole %, or 100 mole % of terephthalic acid and/or dimethyl terephthalate and/or these. A mixture of can be used.

In addition to the terephthalic acid and/or dimethyl terephthalate moieties, the dicarboxylic acid component of the rigid polyesters useful in the present invention may be present in an amount of up to 50 mole %, up to 40 mole %, up to 30 mole %, up to 20 mole %, up to 10 mole %, 5 mole % or less. It may include up to mole percent, or up to 1 mole percent, of one or more modified aromatic dicarboxylic acids. Another embodiment contains 0 mole percent modified aromatic dicarboxylic acid. Accordingly, the amount of one or more modifying aromatic dicarboxylic acids, if present, ranges from any of the preceding endpoints, for example 0.01 to 30 mole %, 0.01 to 20 mole %, 0.01 to 10 mole %, 0.01 to 5 mole %. , or 0.01 to 1 mole percent of one or more modified aromatic dicarboxylic acids. In one embodiment, modified aromatic dicarboxylic acids that can be used in the present invention include, but are not limited to, those having 20 or fewer carbon atoms. Examples of modified aromatic dicarboxylic acids that can be used in the present invention include, but are not limited to, isophthalic acid, 4,4-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalene. Includes dicarboxylic acid, trans-4,4-stilbendicarboxylic acid, and their esters. In one embodiment, isophthalic acid is a modified aromatic dicarboxylic acid. In one embodiment, dimethyl isophthalate is used. In one embodiment dimethyl naphthalate is used.

The carboxylic acid component of the rigid polyester useful in the present invention may comprise up to 10 mole %, for example up to 5 mole % or up to 1 mole % of one or more aliphatic dicarboxylic acids having 2 to 16 carbon atoms, such as malonic acid, succinic acid, glue, etc. Taric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid dicarboxylic acid or their corresponding esters, such as, but not limited to, dimethyl adipate, dimethyl glutarate and dimethyl succinate. It can be further modified. Certain embodiments may also include at least 0.01 mole %, such as at least 0.1 mole %, at least 1 mole %, at least 5 mole %, or at least 10 mole % of one or more modified aliphatic dicarboxylic acids. Another embodiment contains 0 mole percent modified aliphatic dicarboxylic acid. Accordingly, it is contemplated that the amount of one or more modifying aliphatic dicarboxylic acids, if present, may range from any of the preceding endpoints, for example from 0.01 to 10 mole percent, or from 0.1 to 10 mole percent. The total mole percent of dicarboxylic acid components is 100 mole percent.

In one embodiment, instead of dicarboxylic acids, only esters of terephthalic acid and esters of other modified dicarboxylic acids may be used. Suitable examples of dicarboxylic acid esters include, but are not limited to, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the ester is selected from at least one of methyl, ethyl, propyl, and phenyl esters.

In one embodiment of the invention, the rigid polyesters useful in the invention may contain less than 30 mole percent of one or more modified glycols. In another embodiment, polyesters useful in the present invention may contain up to 20 mole percent of one or more modifying glycols. In another embodiment, the rigid polyesters useful in the present invention may contain up to 10 mole percent of one or more modifying glycols. In another embodiment, polyesters useful in the present invention may contain up to 5 mole percent of one or more modifying glycols. In another embodiment, rigid polyesters useful in the present invention may contain 0 mole percent modified glycol. Certain embodiments may also contain at least 0.01 mole %, such as at least 0.1 mole %, or at least 1 mole % of one or more modifying glycols. Accordingly, it is contemplated that the amount of one or more modifying glycols, if present, may range from any of the preceding endpoints, for example from 0.01 to 15 mole percent, or from 0.1 to 10 mole percent.

Modifying glycols useful in the rigid polyesters useful in the present invention may contain from 2 to 16 carbon atoms. For TMCD-CHDM rigid polyester (a polymer containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol and terephthalic acid residues), the modifying glycol is ethylene. It may be a residue of glycol. Examples of other suitable modifying glycols useful in the polyesters described herein include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, isosorbide, propane-1,3-diol, butane-1,4- Diol, 2,2-dimethylpropane-1,3-diol (neopentyl glycol), 2,2,4,4,-tetramethyl-1,3-cyclobutanediol, pentane-1,5- Diol, hexane-1,6-diol, 1,4-cyclohexanedimethanol, 3-methyl-pentanediol-(2,4), 2-methylpentanediol-(1,4), 2, 2,4-tri-methylpentane-diol-(1,3), 2-ethylhexanediol-(1,3), 2,2-diethylpropane-diol-(1,3), hexanediol-(1,3) All-(1,3), 1,4-di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1, 1,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)-propane, 2,2-bis-(4-hydroxypropoxyphenyl)-propane and these Contains mixtures.

In one TMCD rigid polyester embodiment, ethylene glycol is excluded as a modifying diol. For modified PETG and modified PCTG polymers, the modifying glycol may be, for example, a glycol other than ethylene glycol and 1,4-cyclohexanedimethanol.

Rigid polyesters useful in the polyester compositions of the present invention may contain, based on the total mole percent of diol or diacid moieties, 0 to 10 mole percent of one or more branching agents, e.g., a total of 100 mole percent of each diol and 0.01 to 5 mole %, or 0.01 to 4 mole %, or 0.01 to 3 mole %, or 0.01 mole % to 2 mole %, or 0.01 to about 1.5 mole %, or 0.01 to 1 mole %, based on 100 mole % of the diacid. mole %, or 0.1 to 5 mole %, or 0.1 to 4 mole %, or 0.1 to 3 mole %, or 0.1 to 2 mole %, or 0.1 to about 1.5 mole %, or 0.1 to 1 mole %, or 0.5 to 5 mole %. mole %, or 0.5 to 4 mole %, or 0.5 to 3 mole %, or 0.5 to 2 mole %, or 0.5 to about 1.5 mole %, or 0.5 to 1 mole %, or 1 to 5 mole %, or 1 to 4 mole %. mole %, or 1 to 3 mole %, or 1 to 2 mole %, or 0.1 to 0.7 mole %, or 0.1 to 0.5 mole % of a branch each having three or more carboxyl substituents, hydroxyl substituents, or combinations thereof. branching monomers (also referred to herein as branching agents). In certain embodiments, branching monomers or branching agents may be added before and/or during and/or after polymerization of the rigid polyester. Accordingly, the rigid polyester(s) useful in the present invention may be linear or branched.

Examples of branching monomers include, but are not limited to, polyfunctional acids or polyfunctional alcohols, such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, trimethylolethane, glycerol, Contains pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, pentaerythritol, sorbitol, 1,2,6-hexanetriol, glycerin tetramaleic anhydride, trimesic acid, or mixtures thereof. .

In one embodiment, at least one of trimellitic acid, trimellitic anhydride, trimesic acid, pentaerythritol, glycerin, tetramaleic anhydride, and trimeric acids may be used as the branching agent. Branching monomers may be added to the rigid polyester reaction mixture or blended with the rigid polyester in the form of a concentrate, as described, for example, in U.S. Pat. Nos. 5,654,347 and 5,696,176.

Rigid polyesters useful in the present invention may include 1,4-cyclohexanedimethanol moieties in any amount, including, but not limited to, at least one of the following amounts: 0.01 to 100 mole percent; 0.01 to 99.99 mol%; 0.10 to 99 mol%; 0.10 to 95 mol%; 0.10 to 90 mol%; 0.10 to 85 mol%; 0.10 to 80 mol%; 0.10 to 70 mol%; 0.10 to 60 mol%; 0.10 to 50 mol%; 0.10 to 40 mol%; 0.10 to 35 mol%; 0.10 to 30 mol%; 0.10 to 25 mol%; 0.10 to 20 mol%; 0.10 to 15 mol%; 0.10 to 10 mol%; 0.10 to 5 mol%; 1 to 100 mol%; 1 to 99 mol%; 1 to 95 mol%; 1 to 90 mol%; 1 to 85 mol%; 1 to 80 mol%; 1 to 70 mol%; 1 to 60 mol%; 1 to 50 mol%; 1 to 40 mol%; 1 to 35 mol%; 1 to 30 mol%; 1 to 25 mol%; 1 to 20 mol%; 1 to 15 mol%; 1 to 10 mol%; 1 to 5 mol%; 5 to 100 mol%; 5 to 99 mol%; 5 to 95 mol%; 5 to 90 mol%; 5 to 85 mol%; 5 to 80 mol%; 5 to 70 mol%; 5 to 60 mol%; 5 to 50 mol%; 5 to 40 mol%; 5 to 35 mol%; 5 to 30 mol%; 5 to 25 mol%; 5 to 20 mol%; and 5 to 15 mol%; 5 to 10 mol%; 10 to 100 mol%; 10 to 99 mol%; 10 to 95 mol%; 10 to 90 mol%; 10 to 85 mol%; 10 to 80 mol%; 10 to 70 mol%; 10 to 60 mol%; 10 to 50 mol%; 10 to 40 mol%; 10 to 35 mol%; 10 to 30 mol%; 10 to 25 mol%; 10 to 20 mol%; 10 to 15 mol%; 20 to 100 mol%; 20 to 99 mol%; 20 to 95 mol%; 20 to 90 mol%; 20 to 85 mol%; 20 to 80 mol%; 20 to 70 mol%; 20 to 60 mol%; 20 to 50 mol%; 20 to 40 mol%; 20 to 35 mol%; 20 to 30 mol%; and 20 to 25 mol%; 30 to 100 mol%; 30 to 99 mol%; 30 to 95 mol%; 30 to 90 mol%; 30 to 85 mol%; 30 to 80 mol%; 30 to 70 mol%; 30 to 60 mol%; 30 to 50 mol%; 30 to 40 mol%; 30 to 35 mol%; 40 to 100 mol%; 40 to 99 mol%; 40 to 95 mol%; 40 to 90 mol%; 40 to 85 mol%; 40 to 80 mol%; 40 to 70 mol%; 40 to 60 mol%; 40 to 50 mol%; 50 to 100 mol%; 50 to 99 mol%; 50 to 95 mol%; 50 to 90 mol%; 50 to 85 mol%; 50 to 80 mol%; 50 to 70 mol%; 50 to 60 mol%; 60 to 100 mol%; 60 to 99 mol%; 60 to 95 mol%; 60 to 90 mol%; 60 to 85 mol%; 60 to 80 mol%; 60 to 70 mol%; 70 to 100 mol%; 70 to 99 mol%; 70 to 95 mol%; 70 to 90 mol%; 70 to 85 mol%; 70 to 80 mol%; 60 to 70 mol%; 80 to 100 mol%; 80 to 99 mol%; 80 to 95 mol%; 80 to 90 mol%; 90 to 100 mol%; 90 to 99 mol%; 90 to 95 mol%; 95 to 100 mol%; or 95 to 99 mol%.

Rigid polyesters useful in the present invention include polyethylene terephthalate (PET), acid-modified polyethylene terephthalate (PETA), glycol-modified PET (PETG), glycol-modified poly(cyclohexylene dimethylene terephthalate). (PCTG), poly(cyclohexylene dimethylene terephthalate) (PCT), acid-modified poly(cyclohexylene) dimethylene terephthalate) (PCTA), and 2,2,4,4-tetramethylcyclobutane. It may be any of the traditional compositions described as any of the above-described polymers modified with -1,3-diol.

In one embodiment, the rigid polyester useful in the polyester compositions of the present invention comprises an isosorbide moiety. In one embodiment, the isosorbide polymer may also include moieties of ethylene glycol and/or cyclohexanedimethanol. In embodiments, the rigid polyester comprises residues of isosorbide and 1,4-cyclohexanedimethanol, and optionally, ethylene glycol. In embodiments, the rigid polyester comprises the residues of isosorbide and ethylene glycol, and optionally 1,4-cycloehexanedimethanol.

In the case of terephthalate-based rigid polyester, terephthalic acid may be present in an amount of 70 to 100 mol%. The modified dicarboxylic acid may be present in an amount of up to 30 mole percent. In one embodiment, the modifying dicarboxylic acid can be isophthalic acid. Aliphatic diacids may also be present in the terephthalic acid-based polyesters of the present invention.

In certain embodiments, the polyester composition of the present invention comprises 70 to 100 mole % of terephthalic acid residues, and optionally, 0.01 to 30 mole %, or 0.01 to 20 mole %, or 0.01 to 10 mole %, or 0.01 to 5 mole %. hard copolyesters comprising mole percent isophthalic acid residues, or esters thereof and/or mixtures thereof.

In certain embodiments, the polyester composition of the present invention may include a rigid copolyester comprising 1,4-cyclohexanedimethanol, and optionally, ethylene glycol. In certain embodiments, the polymer compositions of the present invention have 50 mole % to 100 mole %, or 60 mole % to 100 mole %, or 65 mole % to 100 mole %, or 70 mole % to 100 mole %, or 75 mole % % to 100 mole %, or 80 mole % to 100 mole %, or 90 mole % to 100 mole %, or 95 mole % to 100 mole % of the residues of 1,4-cyclohexanedimethanol, and optionally 0 mole %. to 50 mole %, or 0 mole % to 40 mole %, or 0 mole % to 35 mole %, or 0 mole % to 30 mole %, or 0 mole % to 25 mole %, or 0 mole % to 20 mole %, or a rigid copolyester comprising 0 mole % to 10 mole %, or 0 mole % to 5 mole % ethylene glycol residues.

In certain embodiments, the polyester compositions of the present invention may comprise a rigid copolyester comprising 99 to 100 mole percent terephthalic acid residues and 99 to 100 mole percent 1,4-cyclohexanedimethanol residues. In certain embodiments, the rigid polyester includes diethylene glycol moieties. In embodiments, the rigid polyester comprises moieties of terephthalic acid, isophthalic acid, and 1,4-cyclohexanedimethanol. In embodiments, the rigid polyester comprises 50 mole % to 99.99 mole % 1,4-cyclohexanedimethanol residues, 0.01 mole % to 50 mole % ethylene glycol residues, and 70 mole % to 100 mole % terephthalic acid. contains residues. In embodiments, the rigid polyester comprises from 80 mole % to 99.99 mole % 1,4-cyclohexanedimethanol residues and from 0.01 mole % to 20 mole % ethylene glycol residues. In embodiments, the rigid polyester comprises from 90 mole % to 99.99 mole % 1,4-cyclohexanedimethanol residues and from 0.01 mole % to 10 mole % ethylene glycol residues. In embodiments, the rigid polyester comprises from 95 mole % to 99.99 mole % 1,4-cyclohexanedimethanol residues and from 0.01 mole % to 5 mole % ethylene glycol residues. In embodiments, the rigid polyester has 95 mole % to 99.99 mole % 1,4-cyclohexanedimethanol residues, 0.01 mole % to 10 mole % ethylene glycol residues, and 90 mole % to 100 mole % terephthalic acid residues. and 0.01 to 10 mole percent of isophthalic acid residues. In embodiments, the rigid polyester has 95 mole % to 100 mole % 1,4-cyclohexanedimethanol residues, 0.01 mole % to 5 mole % ethylene glycol residues, and 95 mole % to 100 mole % terephthalic acid residues. and 0.01 to 5 mole percent of isophthalic acid residues. In embodiments, the rigid polyester consists essentially of the residues of terephthalic acid or an ester thereof and 1,4-cyclohexanedimethanol. In embodiments, the rigid polyester consists essentially of residues of terephthalic acid or an ester thereof, 1,4-cyclohexanedimethanol, and ethylene glycol. In embodiments, the rigid polyester has 0 mole % to 30 mole %, or 0 mole % to 20 mole %, or 0 mole %, based on a total of 100 mole % acid residues and a total of 100 mole % diol residues. mole % to 10 mole %, or 0 mole % to 5 mole %, or 0.01 mole % to 30 mole %, or 0.01 mole % to 20 mole %, or 0.01 mole % to 10 mole %, or 0.01 mole % to 5 mole %. It contains an isophthalic acid residue. In embodiments, the rigid polyester has from 20 mole % to less than 50 mole % 1,4-cyclohexanedimethanol residues, from greater than 50 mole % to 80 mole % ethylene glycol residues, and from 70 mole % to 100 mole % It contains a terephthalic acid residue. In embodiments, the rigid polyester comprises 20 mole % to 40 mole % 1,4-cyclohexanedimethanol residues, 60 mole % to 80 mole % ethylene glycol residues, and 70 mole % to 100 mole % terephthalic acid. contains residues. In embodiments, the rigid polyester comprises 25 mole % to 40 mole % 1,4-cyclohexanedimethanol residues, 60 mole % to 75 mole % ethylene glycol residues, and 70 mole % to 100 mole % terephthalic acid. contains residues. In embodiments, the rigid polyester comprises 25 mole % to 35 mole % 1,4-cyclohexanedimethanol residues, 65 mole % to 75 mole % ethylene glycol residues, and 70 mole % to 100 mole % terephthalic acid. contains residues. In embodiments, the rigid polyester comprises 0 to 20 mole percent 1,4-cyclohexanedimethanol residues and 80 to 100 ethylene glycol residues.

In certain embodiments, the rigid polyester includes neopentyl glycol moieties. In embodiments, the rigid polyester comprises a 2,2,4,4-cyclobutanediol-1,3-cyclobutanediol moiety.

In embodiments, the rigid polyester comprises 0.01 to 99 mole percent of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 0.01 to 99 mole percent of 1,4-cyclohexanediol residues. methanol residues and 70 to 100 mole % of terephthalic acid residues. In embodiments, the rigid polyester comprises 20 to 40 mole percent of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 20 to 40 mole percent of 1,4-cyclohexanediol residues. Methanol residues, 20 to 60 mol% ethylene and glycol residues. In embodiments, the rigid polyester comprises 0.01 to 15 mole percent of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. In embodiments, the rigid polyester contains 15 to 40 mole percent of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 85 mole percent of 1,4-cyclohexanediol residues. Contains a methanol moiety. In embodiments, the rigid polyester comprises 20 to 40 mole percent 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 80 mole percent 1,4-cyclohexanediol residues. Contains a methanol moiety. In embodiments, the rigid polyester comprises 20 to 30 mole percent of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 70 to 80 mole percent of 1,4-cyclohexanediol residues. methanol residues and 70 to 100 mole % of terephthalic acid residues. In embodiments, the rigid polyester comprises 30 to 40 mole percent 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 60 to 70 mole percent 1,4-cyclohexanediol residues. methanol residues and 70 to 100 mole % of terephthalic acid residues.

In embodiments, the rigid polyester component comprises a moiety of 1,4-cyclohexanedicarboxylic acid or an ester thereof. In embodiments, the rigid polyester component comprises a dimethyl-1,4-cyclohexanedicarboxylate moiety. In embodiments, the rigid polyester component has 70 to 100 mole percent, or 80 to 100 mole percent, or 90 to 100 mole percent, based on a total of 100 mole percent acid residues and a total of 100 mole percent diol residues. %, or 95 to 100 mole %, or 98 to 100 mole %.

In some embodiments of the invention, the rigid copolyester useful in the invention comprises a diacid component comprising at least 70 mole percent of the residues of terephthalic acid, isophthalic acid, or mixtures thereof; and a diol component containing a 2,2,4,4-tetramethyl-1,3-cyclobutanediol residue and a 1,4-cyclohexanedimethanol residue (TMCD copolyester).

In one embodiment, the rigid polyester comprises 0.01 to 99.99 mole percent of 2,2,4,4-tetramethyl-1, based on a total of 100 mole percent acid residues and a total of 100 mole percent diol residues. ,3-cyclobutanediol residues and 99.99 to 0.01 mol% of 1,4-cyclohexanedimethanol residues, or 20 to 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol. ol residues and 50 to 80 mole % of 1,4-cyclohexanedimethanol residues, or 20 to less than 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 50 mole % 80 mol% of 1,4-cyclohexanedimethanol residues, or 15 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 85 mol% of 1, 4-cyclohexanedimethanol residues, or 20 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 80 mol% of 1,4-cyclohexanedimethanol. residues, or 20 to 30 mole percent of the residues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 80 mole percent of the residues of 1,4-cyclohexanedimethanol, or 30 to 40 mole percent. mole percent of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 70 mole percent of 1,4-cyclohexanedimethanol residues, or 0.01 to 15 mole percent of 2,2 ,4,4-tetramethyl-1,3-cyclobutanediol residues and 85 to 99.99 mol% of 1,4-cyclohexanedimethanol residues, or 20 to 40 mol% of 2,2,4,4-tetra methyl-1,3-cyclobutanediol residues, 20 to 40 mole percent of 1,4-cyclohexanedimethanol residues and 20 to 60 mole percent ethylene glycol residues, and for all such ranges, optionally, 70 to 70 mole percent. It may contain 100 mole percent of terephthalic acid or isophthalic acid residues or mixtures thereof.

In one embodiment, the rigid polyester comprises 20 to 40 mole percent 2,2,4,4-tetramethyl-1, based on a total of 100 mole percent acid residues and a total of 100 mole percent diol residues. , 3-cyclobutanediol residues and 60 to 80 mol% of 1,4-cyclohexanedimethanol residues and 70 to 100 mol% of terephthalic acid residues.

In certain embodiments, the rigid polyesters of the present invention may comprise copolyesters comprising diacid and diol components, wherein one or more of the diacids is terephthalic acid and isophthalic acid, or esters thereof and/or mixtures thereof. is selected from the group consisting of; The diol component is (a) 20 to less than 50 mol % of 1,4-cyclohexanedimethanol residues and 50 to 80 mol % of ethylene glycol residues, or 20 to 40 mol % of 1,4-cyclohexanedimethyl alcohol. methanol residues and 60 to 80 mole % ethylene glycol residues, or 20 to 40 mole % 1,4-cyclohexanedimethanol residues and 60 to 80 mole % ethylene glycol residues, or 25 to 40 mole % 1,4 -cyclohexanedimethanol residues and 60 to 75 mole % ethylene glycol residues, or 25 to 35 mole % 1,4-cyclohexanedimethanol residues and 65 to 75 mole % ethylene glycol residues (PETG); or (b) 50 mole % to 99.99 mole %, or 55 mole % to 99.99 mole %, or 60 mole % to 99.99 mole %, or 65 mole % to 99.99 mole %, or 70 mole % to 99.99 mole %, or 75 mole % from 80 mol% to 99.99 mol%, or from 85 mol% to 99.99 mol%, or from 90 mol% to 99.99 mol%, or from 95 mol% to 99.99 mol% of 1,4-cyclohexanedi. methanol residue and 0.01 mol% to 50 mol%, or 0.01 mol% to 45 mol%, or 0.01 mol% to 40 mol%, or 0.01 mol% to 35 mol%, or 0.01 mol% to 30 mol%, or 0.01 mole % to 25 mole %, or 0.01 mole % to 20 mole %, or 0.01 mole % to 15 mole %, or 0.01 mole % to 10 mole %, or 0.01 mole % to 5 mole % ethylene glycol (PCTG) residues; or (c) 95 to 99.99 mole % of 1,4-cyclohexanedimethanol residues and 0.01 to 10 mole %, or 0.01 to 5 mole % of isophthalic acid residues and 0.01 to 10 mole %, or 0.01 to 5 mole % ethylene glycol (PCTA) residues, or (d) 0 to 20 mole percent of 1,4-cyclohexanedimethanol residues and 80 to 100 mole percent ethylene glycol (PET or glycol-modified PET) residues, or (e) 1,4-cyclohexanedimethanol, and optionally, an isosorbide polymer comprising ethylene glycol, or (f) an isosorbide polymer comprising ethylene glycol, or (g) (PCT as defined herein). do. In certain embodiments, the diol component is present in an amount of from 10 mole % to 40 mole %, or from 15 mole % to 35 mole %, or from 20 mole % to 35 mole %, or from 20 mole % to 30 mole %, or from 20 mole % 40 mol%, or 20 mol% to 35 mol% isosorbide residues; 30 mol% to 70 mol%, or 40 mol% to 70 mol%, or 45 mol% to 65 mol%, or 45 mol% to 60 mol%, or 45 mol% to 55 mol%, or 47 mol% to 65 mol%. mole %, or 48 mole % to 65 mole %, or 49 mole % to 65 mole %, or 50 mole % to 65 mole %, or 47 mole % to 60 mole %, or 48 mole % to 60 mole %, or 49 mole % mole % to 60 mole %, or 50 mole % to 60 mole % of 1,4-cyclohexanedimethanol residues, and optionally, 0 mole % to 40 mole %, or 0 mole % to 35 mole %, or 0 mole % to 30 mole %, or 0 mole % to 25 mole %, or 0 mole % to 20 mole %, or 0 mole % to 15 mole %, or 0 mole % to 10 mole %, or 0 mole % to 5 mole % It may contain an ethylene glycol residue. In one embodiment, the diol component comprises 18 mole % to 35 mole %, or 20 mole % to 35 mole % isosorbide residues; 40 mol% to 58 mol%, or 45 mol% to 55 mol% of 1,4-cyclohexanedimethanol residues; and 15 mole % to 25 mole %, or 20 mole % to 25 mole % ethylene glycol residues.

In embodiments of the invention, the rigid polyester may comprise residues of a branching agent. In embodiments, the polyester component of the polyester or polyester ether contains 0.01 to 5 mole %, 0.01 to 4 mole, based on a total of 100 mole% acid residues and a total of 100 mole% diol residues. %, 0.01 to 3 mole %, or 0.01 to 2 mole %, or 0.01 to about 1.5 mole %, or 0.01 to 1 mole %, or 0.1 to 5 mole %, or 0.1 to 4 mole %, or 0.1 to 3 mole %, or 0.1 to 2 mole %, or 0.1 to about 1.5 mole %, or 0.1 to 1 mole %, or 0.5 to 5 mole %, or 0.5 to 4 mole %, or 0.5 to 3 mole %, or 0.5 to 2 mole %, or 0.5 to about 1.5 mole %, or 0.5 to 1 mole %, or 1 to 5 mole %, or 1 to 4 mole %, or 1 to 3 mole %, or 1 to 2 mole % of one or more branching agents or one or more Contains a multifunctional branching agent. In embodiments, the multifunctional branching agent has three or more carboxyl or hydroxyl groups. In embodiments, the multifunctional branching agent is selected from the group consisting of trimellitic acid, trimellitic anhydride, trimesic acid, trimethylol ethane, trimethylol propane, pentaerythritol, glycerin, tetramaleic anhydride, and trimeric acid. contains residues. In embodiments, the multifunctional branching agent comprises a moiety of trimellitic anhydride, trimethylol propane, pentaerythritol, glycerin, tetramaleic anhydride.

For certain embodiments of the invention, the rigid polyester useful in the invention is phenol/tetrachloroethane (60/40 (wt/wt)) at a concentration of 0.5 g/100 mL at 25°C, according to ASTM D4603. When determined, it can exhibit at least one of the following ranges of intrinsic viscosity: 0.35 to 1.5 dL/g; 0.35 to 1.2 dL/g; 0.35 to 1 dL/g; 0.50 to 1.5 dL/g; 0.50 to 1.2 dL/g; 0.50 to 1 dL/g; 0.50 to 0.95 dL/g, 0.50 to 0.90 dL/g, 0.50 to 0.85 dL/g; 0.50 to 0.80 dL/g; 0.50 to 0.75 dL/g; less than 0.50 to 0.75 dL/g; 0.50 to 0.72 dL/g; 0.50 to 0.70 dL/g; less than 0.50 to 0.70 dL/g; 0.50 to 0.68 dL/g; less than 0.50 to 0.68 dL/g; 0.50 to 0.65 dL/g; 0.55 to 1.5 dL/g; 0.55 to 1.2 dL/g; 0.55 to 1 dL/g; 0.55 to 0.85 dL/g; 0.55 to 0.80 dL/g; 0.55 to 0.78 dL/g; 0.55 to 0.75 dL/g; less than 0.55 to 0.75 dL/g; 0.55 to 0.72 dL/g; 0.55 to 0.70 dL/g; less than 0.55 to 0.70 dL/g; 0.55 to 0.68 dL/g; less than 0.55 to 0.68 dL/g; 0.55 to 0.65 dL/g; 0.60 to 1.5 dL/g; 0.60 to 1.3 dL/g; 0.60 to 1.2 dL/g; 0.60 to 1.1 dL/g; 0.60 to 1.0 dL/g; 0.60 to 0.95 dL/g; 0.60 to 0.90 dL/g; 0.60 to 0.85 dL/g; 0.60 to 0.80 dL/g; 0.60 to 0.75 dL/g; 0.60 to 0.68 dL/g; 0.70 to 1.5 dL/g; 0.70 to 1.2 dL/g; 0.80 to 1.5 dL/g; or 0.80 to 1.2 dL/g.

Unless otherwise stated, it is contemplated that the rigid polyesters of the present invention may have at least one of the intrinsic viscosity ranges described herein and at least one of the monomer ranges for the compositions described herein. It is also contemplated that the rigid polyesters of the present invention, unless otherwise noted, may have at least one of the T _g ranges described herein and at least one of the monomer ranges for the compositions described herein. Additionally, the rigid polyesters of the present invention, unless otherwise specified, may have at least one of the T _g ranges described herein, at least one of the intrinsic viscosity ranges, and at least one of the monomer ranges for the compositions described herein. It is considered to exist.

In another embodiment of the invention, the rigid polyester comprises one or more diacid moieties selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and cyclohexane dicarboxylic acid; and one or more selected from the group consisting of ethylene glycol, diethylene glycol, cyclohexane dimethanol, 2,2,4,4-tetramethyl cyclobutane 1,3-diol, isosorbide, neopentyl glycol, and butane diol. Contains diol.

The amount of hard polyester in the polyester composition may range from about 1 to about 99% by weight based on the weight of the polyester composition. In other embodiments, the amount of rigid polyester in the polyester composition is about 10 to about 90%, about 20 to about 80%, about 30 to about 70%, about 40 to about 40% by weight, based on the weight of the polyester composition. It may be in the range of about 60% by weight.

polyester elastomer

The polyester elastomer used in the polyester composition of the present invention may be any known in the art having a T _g of 50°C or less. In one embodiment, the polyester elastomer comprises one or more dicarboxylic acids; one or more dihydroxy alcohols; one or more polyols; and optionally a polyfunctional acid, alcohol or anhydride branching agent, wherein the polyester elastomer has a T _g of 50° C. or less. In other embodiments, the T _g of the polyester elastomer is 45°C or lower, 40°C or lower, 35°C or lower, 30°C or lower, 25°C or lower, 20°C or lower, 15°C or lower, 10°C or lower, 5°C or lower, 0℃ or lower, -5℃ or lower, -10℃ or lower, -15℃ or lower, -20℃ or lower, -25℃ or lower, -30℃ or lower, -35℃ or lower, -40℃ or lower, -50℃ or lower, - It may be 55°C or lower, -60°C or lower, -70°C or lower, or -80°C or lower. T _g of the polyester elastomer is 50°C to -80°C, 45°C to -80°C, 40°C to -80°C, 35°C to -80°C, 30°C to -80°C, 25°C to -80°C. , 20°C to -80°C, 15°C to -80°C, 10°C to -80°C, 5°C to -80°C, 0°C to -80°C, -5°C to -80°C, -10°C to -80°C ℃, -15℃ to -80℃, -20℃ to -80℃, -25℃ to -80℃, -30℃ to -80℃, -40℃ to -80℃, -50℃ to -80℃, -60°C to -80°C, 50°C to -75°C, 45°C to -75°C, 40°C to -75°C, 35°C to -75°C, 30°C to -75°C, 25°C to -75°C, 20°C to -75°C, 15°C to -75°C, 10°C to -75°C, 5°C to -75°C, 0°C to -75°C, -5°C to -75°C, -10°C to -75°C , -15℃ to -75℃, -20℃ to -75℃, -25℃ to -75℃, -30℃ to -75℃, -40℃ to -75℃, -50℃ to -75℃, - 60°C to -75°C, 50°C to -70°C, 45°C to -70°C, 40°C to -70°C, 35°C to -70°C, 30°C to -70°C, 25°C to -70°C, 20 ℃ to -70℃, 15℃ to -70℃, 10℃ to -70℃, 5℃ to -70℃, 0℃ to -70℃, -5℃ to -70℃, -10℃ to -70℃, -15℃ to -70℃, -20℃ to -70℃, -25℃ to -70℃, -30℃ to -70℃, -40℃ to -70℃, -50℃ to -70℃, -60℃ It may range from ℃ to -70℃.

The polyester elastomer has a temperature of less than 1000 Mpa, less than 950 Mpa, less than 900 Mpa, less than 850 Mpa, less than 800 Mpa, less than 750 Mpa, less than 700 Mpa, less than 650 Mpa, less than 650 Mpa at 25°C, according to ASTM D790. Less than, less than 600 Mpa, less than 550 Mpa, less than 500 Mpa, less than 450 Mpa, less than 400 Mpa, less than 350 Mpa, less than 300 Mpa, less than 250 Mpa, less than 200 Mpa, less than 150 Mpa, less than 100 Mpa, less than 50 Mpa It may have a flexural modulus. In other embodiments of the invention, the polyester elastomer has a temperature of 25 Mpa to 1000 Mpa, 50 Mpa to 1000 Mpa, 100 Mpa to 1000 Mpa, 150 Mpa to 1000 Mpa, 200 Mpa at 25°C according to ASTM D790. to 1000 Mpa, 250 Mpa to 1000 Mpa, 300 Mpa to 1000 Mpa, 350 Mpa to 1000 Mpa, 400 Mpa to 1000 Mpa, 450 Mpa to 1000 Mpa, 500 Mpa to 1000 Mpa, 550 Mpa to 1000 Mpa, 600 Mpa to 10 00 Mpa, 650 Mpa to 1000 Mpa, 700 Mpa to 1000 Mpa, 750 Mpa to 1000 Mpa, 800 Mpa to 1000 Mpa, 25 Mpa to 9000 Mpa, 50 Mpa to 900 Mpa, 100 Mpa to 900 Mpa, 150 Mpa to 900 Mpa, 200 Mpa to 900 Mpa, 250 Mpa to 900 Mpa, 300 Mpa to 900 Mpa, 350 Mpa to 900 Mpa, 400 Mpa to 900 Mpa, 450 Mpa to 900 Mpa, 500 Mpa to 900 Mpa, 550 Mpa to 900 Mpa, 600 Mpa to 900 Mpa, 650 Mpa to 900 Mpa, 700 Mpa to 900 Mpa, 750 Mpa to 900 Mpa, 25 Mpa to 800 Mpa, 50 Mpa to 800 Mpa, 100 Mpa to 800 Mpa, 150 Mpa to 800 Mpa, 200 Mpa to 800 Mpa, 250 Mpa to 800 Mpa, 300 Mpa to 800 Mpa, 350 Mpa to 800 Mpa, 400 Mpa to 800 Mpa, 450 Mpa to 800 Mpa, 500 Mpa to 800 Mpa, 550 Mpa to 800 Mpa, 600 Mpa to 800 Mpa, 650 Mpa to 800 Mpa, 700 Mpa to 800 Mpa, 25 Mpa to 700 Mpa, 50 Mpa to 700 Mpa, 100 Mpa to 700 Mpa, 150 Mpa to 700 Mpa, 200 Mpa to 700 Mpa, 250 Mpa to 700 Mpa, 300 Mpa It may have a flexural modulus ranging from 700 Mpa to 700 Mpa, 350 Mpa to 700 Mpa, 400 Mpa to 700 Mpa, 450 Mpa to 700 Mpa, 500 Mpa to 700 Mpa, 550 Mpa to 700 Mpa, or 600 Mpa to 700 Mpa.

In some embodiments of the invention, the polyester elastomer comprises the moiety of one or more dicarboxylic acid compounds, diester derivatives thereof, anhydrides thereof, or combinations thereof. The dicarboxylic acid compound can form an ester linkage with a diol or polyol compound.

In some embodiments of the invention, the polyester elastomer is a cycloaliphatic diacid moiety, such as, but not limited to, hexahydrophthalic anhydride (HHPA), tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, 5-norbornene-2, 3-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid, 2,3-norbornedicarboxylic acid, 2,3-norbornedicarboxylic acid anhydride, cyclohexane dicarboxylic acid (1,2-, 1,3- and including 1,4-isomers (CHDA), dimethylcyclohexane (including 1,2-, 1,3- and 1,4-isomers) (DMCD) and mixtures thereof.

In some embodiments of the invention, the polyester elastomer has a non-cyclic aliphatic diacid moiety, such as, but not limited to, adipic acid, maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride. , citraconic acid, dodecanedioic acid, succinic acid, succinic anhydride, glutaric acid, sebacic acid, azelaic acid, and mixtures thereof.

In some embodiments of the invention, the polyester elastomer contains residues of a di-alcohol component, such as, but not limited to, 2,2,4,4-tetraalkylcyclobutane-1,3-diol (e.g., 2 ,2,4,4-tetramethylcyclobutane-1,3-diol), 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,2-cyclohexanedimethanol, 1 ,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, hydroxypivalylhydroxypivalate, 2-methyl-1,3 -Propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4,4-tetramethyl-1,6-hexanediol, 1,10-decanediol, 1,4 -Includes benzenedimethanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol and tetraethylene glycol.

In some embodiments of the invention, the polyester elastomer comprises one or more polyol moieties. The polyols include, but are not limited to, polytetramethylene ether glycol (PTMG), polyethylene glycol, polypropylene glycol, or any other polyether polyol and mixtures thereof. The polyol is an organic compound containing a plurality of hydroxyl groups. Molecules with more than two hydroxyl groups are polyols, those with three are triols, those with four are tetrols, etc. By convention, polyol does not refer to compounds containing other functional groups. The polyol typically has a weight average molecular weight (M _w ) of about 500 to 5000, with M _w of about 1000 to 2000 being preferred. In embodiments, the hydroxyl functionality (meaning the number of hydroxyl groups as polymer end groups) may range from about 1.9 to about 2.1 for thermoplastic materials and at least about 2.1 for crosslinked materials.

In some embodiments of the invention, the polyester elastomer may include one or more optional branching agents, such as polyfunctional acids, alcohols, anhydrides, and combinations thereof.

In some embodiments of the invention, the optional branching agent includes, but is not limited to, 1,1,1-trimethylol propane, 1,1,1-trimethylol ethane, glycerin, pentaerythritol, erythritol. , threitol, dipentaerythritol, sorbitol, neopentyl glycol, phenyl dianhydride, hexanediol, trimellitic anhydride (TMA), and combinations thereof.

In some embodiments of the invention, the diacid component of the polyester elastomer may include cyclohexane dicarboxylic acid (CHDA), dimethylcyclohexane (DMCD), and combinations thereof, and the diglycol of the polyester. The ingredients include cyclohexane dimethanol (CHDM) and the polyol includes polytetramethylene ether glycol (PTMG).

In some embodiments of the invention, the diacid component of the polyester elastomer includes cyclohexane dicarboxylic acid (CHDA), dimethyl cyclohexane (DMCD), and combinations thereof, and the diglycol component of the polyester includes Cyclohexane dimethanol (CHDM), the polyol includes polytetramethylene ether glycol (PTMG), and the branching agent includes trimellitic anhydride (TMA).

The polyester elastomer in the polyester composition of the present invention may be a thermoplastic copolyester ether elastomer. The thermoplastic copolyester ether elastomer has high flexibility, very high transparency, excellent toughness and puncture resistance, excellent low-temperature strength, and excellent flex crack and creep resistance even without plasticizers. In one embodiment, the thermoplastic copolyester ether elastomer is poly(cyclohexylene dimethylene cyclohexanedicarboxylate) prepared by reaction of dimethylcyclohexane dicarboxylate with cyclohexane dimethanol and polytetramethylene glycol. )(PCCE).

Accordingly, the present invention relates to elastomeric thermoplastic copolyester ethers, particularly high molecular weight semi-crystalline thermoplastic copolyester ethers prepared by the reaction of dimethylcyclohexane dicarboxylate with cyclohexane dimethanol and polytetramethylene glycol. It relates to the use of polyester compositions that may include phosphorus elastomers. The copolyester ethers useful according to the invention have high flexibility, very high transparency, excellent toughness and puncture resistance, excellent low-temperature strength, and excellent flex crack and creep resistance even without plasticizers.

Copolyester ethers useful in accordance with the present invention include those disclosed in U.S. Pat. Nos. 4,349,469 and 4,939,009, the disclosures of which are incorporated herein by reference. Copolyester ethers useful in accordance with the present invention are tough and flexible materials that can be extruded into transparent sheets. It is a copolyester based on 1,4-cyclohexanedicarboxylic acid or its esters, 1,4-cyclohexanedimethanol, and poly(oxytetramethylene) glycol (also known as polytetramethylene ether glycol) Contains ether. Copolyester ethers useful in accordance with the present invention include those sold under the ECDEL brand name from Eastman Chemical Company (Kingsport, Tenn.).

In one embodiment, the copolyester ether has an intrinsic viscosity (I.V.), for example, of about 0.8 to 1.5; and (1) a dicarboxylic acid component comprising 1,4-cyclohexanedicarboxylic acid or an ester thereof and typically having a trans isomer content of at least 70%, at least 80%, or at least 85%; and (2) for example, (a) about 95 to about 65 mole percent of 1,4-cyclohexanedimethanol, and (b) about 5 to about 50 mole percent, 10 to 40 mole percent, or 15 to 35 mole percent. Recurring from a glycol component comprising mole percent poly(oxytetramethylene) glycol and having a molecular weight, for example, from about 500 to about 1200, or from 900 to 1,100, in both cases being weight average molecular weights. It can have units.

Alternatively, the copolyester ether may have an I.V., for example, from about 0.85 to about 1.4, or from 0.9 to 1.3, or from 0.95 to 1.2. “I.V.” herein is determined by dissolving a sample of the polymer of interest in a solvent, measuring the flow rate of the solution through a capillary, and then calculating the I.V. based on the flow. Specifically, ASTM D4603-18 (Standard Test Method for Determining Intrinsic Viscosity of Poly(ethylene Terephthalate) (PET) by Glass Capillary Viscometer) can be used to determine the I.V.

In addition to 1,4-cyclohexanedimethanol, other typical aliphatic or cycloaliphatic diols of 2 to 10 carbon atoms useful in forming the copolyester ether include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, Ethylene glycol, 1,2-propylene glycol, 1,4-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2 -Ethyl-2-isobutyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2,4- Trimethyl-1,3-pentanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,2,4,4-tetramethyl-1,6-hexanediol, 1,10-decanediol, 1,4-benzenedimethanol, hydroxypivalyl hydroxypivalate, and combinations thereof. Small amounts of aromatic diols can be used, but this may not be desirable.

In addition to 1,4-cyclohexanedicarboxylic acid, other aliphatic, cycloaliphatic or aromatic diacids or dianhydrides of 2 to 10 carbon atoms useful in forming the copolyester ether include adipic acid, maleic anhydride, maleic acid, fumaric acid, Itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, dodecanedioic acid, succinic acid, succinic anhydride, glutaric acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, stilbene dicarboxylic acid, bibenzoic acid hexahydrate Hydrophthalic anhydride (HHPA), tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid, 2,3-norbornenedicarboxylic acid, 2,3-norbornanedicarboxylic anhydride, dimethylcyclohexane dicarboxylate (DMCD), and combinations thereof. Fatty acids or anhydrides are preferred.

In addition to polytetramethylene ether glycol, other useful polyether polyols having 2 to 4 carbon atoms between ether units include polyethylene ether glycol, polypropylene ether glycol, and combinations thereof. For the purposes of the present invention, the term “polyol” refers to “polymeric diol”. Useful commercial polyether polyols include Carbowax resin, Pluronics resin, and Niax resin. Polyether polyols useful in accordance with the present invention include those that can generally be characterized as polyalkylene oxides and can have molecular weights, for example, from about 300 to about 10,000 or from 500 to 2000.

The copolyester ether is, for example, a polybasic acid or polyhydric alcohol branching agent having 3 or more -COOH or -OH functional groups and 3 to 60 carbon atoms, based on the acid or glycol component. It may be additionally included in an amount of about 1.5 mol% or less. Esters of many of these acids or polyols may also be used. Suitable branching agents include 1,1,1-trimethylol propane, 1,1,1-trimethylolethane, glycerin, pentaerythritol, erythritol, threitol, dipentaerythritol, sorbitol, phenyl dianhydride. Includes water, trimellitic acid or anhydride, trimesic acid, and trimeric acid.

It should be understood that the total acid reactants must be 100% and the total glycol reactants must be 100 mole percent. Although the acid reactant is stated to include 1,4-cyclohexanedicarboxylic acid, if the branching agent is a polybasic acid or anhydride, this is calculated as part of 100 mole percent of the acid. Likewise, although the glycol reactant is stated to include 1,4-cyclohexanedimethanol and poly(oxytetramethylene) glycol, if the branching agent is a polyol, this is calculated as part of 100 mole percent glycol.

To provide polymers that form or crystallize rapidly, the trans and cis isomer content of the final copolyester ether can be controlled. Cis- and trans-isomer contents are determined by conventional methods known to those skilled in the art. See, for example, US Pat. No. 4,349,469.

Particularly suitable copolyester ethers useful according to the invention are copolyesters based on 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanedimethanol and polytetramethylene ether glycol or other polyalkylene oxide glycols. It is ether. In one embodiment, 1,4-cyclohexanedicarboxylic acid is present in at least 50 mole %, at least 60 mole %, at least 70 mole %, at least 75 mole %, in each case based on the total amount of dicarboxylic acid present in the copolyester ether. It is present in an amount of at least 80 mol%, at least 85 mol%, at least 90 mol%, or at least 95 mol%. In another embodiment, 1,4-cyclohexanedimethanol is present in an amount of from about 60 mole % to about 98 mole %, or from 65 mole % to 95 mole %, or from 70 mole % to 90 mole %, in each case based on the total amount of glycol. mole percent, or in an amount of 75 mole percent to 85 mole percent. In another embodiment, the polytetramethylene ether glycol is present in an amount of from about 2 to about 40 mole %, or from 5 mole % to 50 mole %, or from 7 mole % to 48 mole %, in each case based on the total amount of glycol present. or 10 mole % to 45 mole %, or 15 to 40 mole %, or 20 mole % to 35 mole %.

In another embodiment, the amount of 1,4-cyclohexanedicarboxylic acid is from about 100 mole % to about 98 mole %, the amount of 1,4-cyclohexanedimethanol is from about 80 mole % to about 95 mole %, and the polytetramethylene ether Glycol may be present in an amount of from about 5 mole % to about 20 mole % and trimellitic anhydride may be present in an amount of 0.1 to 0.5 mole % TMA.

In a more specific embodiment, the amount of 1,4-cyclohexanedicarboxylic acid is 98 mole % to 100 mole %, the amount of 1,4-cyclohexanedimethanol is 70 mole % to 95 mole %, and the amount of polytetramethylene ether glycol is: 5 mol% to 30 mol%, and trimellitic anhydride may be present in an amount of 0 to 0.5 mol%.

In another specific embodiment, the amount of 1,4-cyclohexanedicarboxylic acid is 99 mol% to 100 mol%, the amount of 1,4-cyclohexanedimethanol is 70 mol% to 95 mol%, and the amount of polytetramethylene ether glycol The amount is 5 mol% to 30 mol%, and trimellitic anhydride may be present in an amount of 0 mol% to 1 mol%.

The copolyester ether used in the polyester composition of the present invention may contain a phenolic antioxidant that can react with the polymer intermediate. This causes the antioxidant to become chemically attached to the copolyester ether and essentially cannot be extracted from the polymer. Antioxidants useful in the present invention may contain one or more of acid, hydroxyl, or ester groups that can react with the reagents used in the preparation of the copolyester ether. It is preferred that the phenolic antioxidant is in sterically hindered form and is relatively non-volatile. Examples of suitable antioxidants include hydroquinone, arylamine antioxidants such as 4,4'-bis(α,α-dimethylbenzyl)diphenylamine; sterically hindered phenol antioxidants such as 2,6-di-tert-butyl-4-methylphenol, butylated p-phenyl-phenol and 2-(α-methylcyclohexyl)-4,6-dimethylphenol; Bis-phenols, such as 2,2'-methylenebis-(6-tert-butyl-4-methylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 4,4 '-Methylenebis(6-tert-butyl-2-methylphenol), 4,4'-butylene-bis(6-tert-butyl-3-methylphenol), methylenebis-(2,6-di -tertiary-butylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol) and 2,2'-thiobis(4-methyl-6-tert-butylphenol); Tris-phenol, such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)-hexahydro-s-triazine, 1,3,5-trimethyl- Contains 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and tri(3,5-di-tert-butyl-4-hydroxyphenyl)phosphite. and tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)methane] (which is obtained from Irganox 1010 oxidation from Geigy Chemical Company). commercially available as an inhibitor) is preferred. Preferably, the antioxidant is used in an amount of about 0.1 to about 1.0 based on the weight of the copolyester ether.

Copolyester ethers used in the polyester compositions of the present invention include those characterized by excellent melt strength. Polymers with melt strength are described as being able to support themselves when extruded in a molten state downward from a die. If a polymer with melt strength is extruded downward, the melt will hold together. When a polymer without melt strength is extruded downward, the melt falls rapidly and breaks apart. For comparison, melt strength is measured at a temperature of 20°C above the melt peak.

In another embodiment of the present invention, the polyester elastomer is:

a. residues of cyclohexane dicarboxylic acid (CHDA) and dimethylcyclohexane (DMCD);

b. cyclohexane dimethanol (CHDM) moiety,

c. a polytetramethylene ether glycol (PTMG) moiety, and

d. Trimellitic anhydride (TMA) moiety

Includes.

In another embodiment of the invention, the polyester elastomer comprises:

a. 99 to 100 mole percent of a diacid selected from the group consisting of cyclohexane dicarboxylic acid (CHDA), dimethylcyclohexane dicarboxylic acid (DMCD), and combinations thereof, based on the total molar acid content of the polyester;

b. Based on the total glycol content of the polyester, 75 to 92 mole percent cyclohexane dimethanol and 8 to 25 mole percent polytetramethylene ether glycol;

c. Optionally, up to 1 mole percent of a branching agent selected from the group consisting of glycerin, pentaerythritol, phenyl dianhydride, trimellitic anhydride, and combinations thereof, based on the total molar acid content of the polyester.

In another embodiment, the present invention includes a polyester elastomer comprising the following moieties for low shear polymer melt processing:

a. 99 to 100 mole percent of a diacid selected from the group consisting of cyclohexane dicarboxylic acid, dimethylcyclohexane dicarboxylic acid, and combinations thereof, based on the total molar acid content of the polyester;

b. Based on the total glycol content of the polyester, 75 to 92 mole % of 1,4-cyclohexane dimethanol and 4 to 25 mole % of polytetramethylene ether glycol; and

c. Optionally, up to 1 mole percent of a branching agent selected from the group consisting of glycerin, pentaerythritol, phenyl dianhydride, trimellitic anhydride, and combinations thereof, based on the total molar acid content of the polyester.

In another embodiment, the polyester elastomer is Ecdel™ copolyester commercially available from Eastman Chemical Company, which has a molecular weight of 1000 with cyclohexane dicarboxylic acid (CHDA) and cyclohexane dimethanol. It is a copolyester based on a combination of polytetramethylene ether glycol (PTMG 1000). In polyester synthesis processes, CHDA and/or dimethylcyclohexane dicarboxylic acid (DMCD) may be used, depending on the process. Trimellitic anhydride (TMA) can be used up to about 1% in the formulation.

Trimellitic Anhydride (TMA)

1,4-cyclohexane dicarboxylic acid

1,4-dimethylcyclohexane dicarboxylic acid

1,4-cyclohexane dimethanol

Polytetramethylene ether glycol (PTMG)

The amount of polyester elastomer in the polyester composition may range from about 1 to about 99% by weight based on the weight of the polyester composition. In other embodiments, the amount of polyester elastomer in the polyester composition is from about 10 to about 90 weight percent, from about 80 to about 20 weight percent, from about 70 to about 30 weight percent, based on the weight of the polyester portion of the composition. percent by weight, or may range from about 60 to about 40 percent by weight.

The present invention encompasses the use of primary antioxidants, secondary antioxidants and chain extending additives to inhibit thermal oxidation and hydrolysis of polymers maintained at elevated temperatures for extended periods of time and to improve polymer flow. This combination has been shown to be effective for polyester and copolyester series polymers. Improved thermal oxidation and hydrolytic stability can be measured using gel permeation chromatography and through visual color observation and spectrophotography. Viscosity improvement can be measured using parallel plate rheometry.

In one embodiment of the invention, the polyester composition comprises at least one primary antioxidant of the sterically hindered phenol type, at least one secondary antioxidant of the phosphite series, and at least one chain extender having epoxide functionality. do. During exposure to high temperatures, the polymer will undergo chain scission, forming free radical molecules and carboxylic acids, which are highly reactive and will cause auto-catalytic degradation of the polymer. Additionally, free radicals can react in the presence of oxygen to produce hydroxy, peroxy, peroxide, mono and dihydroxy terephthalates, which are also highly reactive and will cause further degradation of the polymer. When primary antioxidants are added, they react with free radicals to inhibit further decomposition or with oxygen to produce hydroxy, peroxy and other oxygen-containing radicals. Secondary antioxidants (also known as oxygen scavengers) react with hydroxy, peroxy and oxygen radicals before they can cause further polymer degradation.

Condensation polymers are also prone to hydrolysis if not pre-dried or if kept at elevated temperatures in humid air for long periods of time. A condensation polymer is any polymer in which monomers are formed together to create a polymer and a by-product (water or methanol) is produced. This polymerization reaction is reversible, so the condensation polymer must be pre-dried before processing.

Primary antioxidant

Sterically hindered phenols and sterically hindered amines are the main types of primary antioxidants used in thermoplastics. Typical hindered phenol and amine structures are as follows:

[In the above equation,

R ₁ and R ₂ are independently selected from the group consisting of H, CH ₃ , CH ₂ (CH ₂ ) _n CH ₃ , C(CH ₃ ) ₃ , and CH(CH ₃ ) ₂ , where n is 0 to 5 , provided that only one of R ₁ and R ₂ may be H,

R ₃ , R ₄ , and R ₅ are independently H or an organic residue],

[In the above equation,

each X is independently selected from the group consisting of C ₁ -C ₂₀ alkyl and C ₁ -C ₂₀ alkenyl;

L, at each occurrence, is absent or independently selected from the group consisting of C ₁ -C ₂₀ alkyl and C ₁ -C ₂₀ alkenyl;

each R ₁ is independently selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkenyl, -O(C ₁ -C ₂₀ alkyl) and -O(C ₁ -C ₂₀ alkenyl); ;

each R ₂ is independently selected from the group consisting of hydrogen, C ₁ -C ₂₀ alkyl and C ₁ -C ₂₀ alkenyl;

each R ₃ is independently selected from the group consisting of hydrogen, C ₁ -C ₂₀ alkyl, and C ₁ -C ₂₀ alkenyl;

n is an integer from 1 to 50].

When selecting a sterically hindered phenol, several characteristics should be considered, including relative phenol content (which affects reactivity) and molecular weight (higher molecular weight is better to ensure that antioxidants do not easily escape from the polymer). Similarly, when selecting a sterically hindered amine, weight efficiency, miscibility and basicity should be considered.

When selecting a sterically hindered phenolic antioxidant, several properties can be considered, including relative phenol content (which affects reactivity) and molecular weight (the higher the better to ensure that the antioxidant does not easily escape from the polymer). there is.

In one embodiment, the phenolic antioxidant may be in sterically hindered form and/or be relatively non-volatile. Examples of suitable phenolic antioxidants include hydroquinone, arylamine antioxidants such as 4,4'-bis(α,α-dimethylbenzyl)diphenylamine; sterically hindered phenol antioxidants such as 2,6-di-tert-butyl-4-methylphenol, butylated p-phenyl-phenol and 2-(α-methylcyclohexyl)-4,6-dimethylphenol; Bis-phenols, such as 2,2'-methylenebis-(6-tert-butyl-4-methylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 4,4 '-Methylenebis(6-tert-butyl-2-methylphenol), 4,4'-butylenebis(6-tert-butyl-3-methylphenol), methylenebis(2,6-di-3 tert-butylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol) and 2,2'-thiobis(4-methyl-6-tert-butylphenol); Tris-phenol, such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)-hexahydro-s-triazine, 1,3,5-trimethyl- 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and tri(3,5-di-tert-butyl-4-hydroxyphenyl)phosphite; and pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], the last of which is Irganox™ 1010 oxidation. It is marketed as an anti-inflammatory agent.

In another embodiment, the primary antioxidant is selected from one or more sterically hindered phenols, one or more secondary aryl amines, or combinations thereof.

In another embodiment, one or more sterically hindered phenols useful in the polyester compositions of the present invention include triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1, 6-hexanediolbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy -3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)prop pionate], 2,2-thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-t- Butyl-4-hydroxyphenyl)propionate, benzenepropanoic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxy-2,2-bis[[3-[3,5-bis (1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediyl ester, N,N'-hexamethylene bis(3,5-di- t-butyl-4-hydroxy-hydrocinnamamide), tetrakis(methylene 3,5-di-tert-butyl-hydroxycinnamate)methane, 4-[[4,6-bis(octylthio)- 1,3,5-triazin-2-yl] amino] -2,6-bis (1,1-dimethylethyl) phenol (Irganox (registered trademark) 565) and octadecyl 3,5-di- and one or more compounds selected from tert-butylhydroxyhydrocinnamates.

In one embodiment, the phenolic antioxidant useful in the polyester compositions of the present invention is octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate (CAS No. 2082 -79-3; Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (CAS No. 6683-198, otherwise known as Irganox™) Also known as 1010), N,N'-hexane-1,6-diyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl]propionamide] (CAS No. 23128 -747-, Irganox (trade name) 1098), benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxyoctadecyl ester (Irganox (trade name) 1076). The Irganox phenolic additive brand is commercially available from BASF. In another embodiment, the sterically hindered phenol is octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl )-propionate.In another embodiment, the one or more sterically hindered phenols are 3,5-bis(1,1-dimethylethyl)-4-hydroxy-2,2-bis[[3-[ It is 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediyl ester.

In one embodiment, the phenolic antioxidant is present in an amount of 0.01 to 5%, or 0.01 to 4%, or 0.01 to 3%, by weight, based on the total weight of 100% by weight of the polymer composition. 0.01% to 2.0% by weight, or 0.01% to 1.0% by weight, or 0.01% to 0.90% by weight, or 0.01% to 0.80% by weight, or 0.01% to 0.75% by weight, or 0.01 to 0.70% by weight. , or 0.01 to 0.60% by weight, or 0.01 to 0.50% by weight, or 0.10 to 5% by weight, or 0.10 to 4% by weight, or 0.10 to 3% by weight, or 0.10 to 2.0% by weight. Weight percent, 0.10 weight percent to 1.0 weight percent, 0.10 weight percent to 0.90 weight percent, 0.10 weight percent to 0.80 weight percent, 0.10 weight percent to 0.75 weight percent, or 0.10 weight percent to 0.70 weight percent, or 0.10 weight percent to 0.60 weight percent. % by weight, or 0.10 % to 0.50 % by weight, or 0.25 % to 5 % by weight, or 0.25 % to 4 % by weight, or 0.25 % to 3 % by weight, or 0.25 % to 2.0 % by weight, or 0.25 % by weight. % to 1.0% by weight, or 0.25% to 0.90% by weight, or 0.25% to 0.80% by weight, or 0.25% to 0.75% by weight, or 0.25% to 0.70% by weight, or 0.25% to 0.60% by weight. %, or 0.25% to 0.50% by weight, or 0.50% to 5% by weight, or 0.50% to 4% by weight, or 0.50% to 3% by weight, or 0.50% to 2.0% by weight, or 0.50% by weight. in an amount of from 1.5% to 1.5% by weight, or from 0.50% to 1.0% by weight, or from 0.50% to 0.90% by weight, or from 0.50% to 0.80% by weight, from 0.50% to 0.75% by weight, or from 0.80% to 1.2% by weight. exists as

In certain embodiments of the invention, the primary antioxidant is present in an amount of 0.01% to 5%, or 0.01% to 4%, or 0.01% to 3%, by weight, based on the total weight of 100% polymer composition. %, or 0.01 to 2.0% by weight, or 0.01 to 1.5% by weight, or 0.01 to 1% by weight, or 0.01 to 0.75% by weight, or 0.01 to 0.50% by weight, or 0.10 to 5% by weight, or 0.10% by weight in an amount of from 4% to 4% by weight, or from 0.10% to 3% by weight, or from 0.10 to 2.0% by weight, or from 0.10 to 1.5% by weight, or from 0.10 to 1% by weight, or from 0.10 to 0.75% by weight, or from 0.10 to 0.60% by weight. (total loading) may be present in the polyester composition of the present invention.

In certain embodiments of the invention, the primary antioxidant is present in an amount of 0.01 to 2.0 weight percent, or 0.10 to 2.0 weight percent, or 0.01 to 1.0 weight percent, or 0.10 to 0.10 weight percent, based on the total weight of the 100 weight percent polyester composition. It may be present in the polyester composition of the present invention in an amount (total loading) of 1.0 wt%, or 0.10 to 1.5 wt%, or 0.50 to 1.5 wt%, or 0.75 to 1.25 wt%, or 0.10 to 60 wt%.

In one embodiment of the invention, the primary antioxidant is present in an amount of 0.01 to 1.0 weight percent, or 0.01 to 0.90 weight percent, or 0.10 to 1.0 weight percent, or 0.10 to 0.90 weight percent, based on the total weight of the polyester composition. , or 0.20 to 1.0 wt%, 0.20 to 0.90 wt%, or 0.25 to 1.0 wt%, or 0.25 to 0.90 wt% (total loading).

As used herein, “sterically hindered amine” refers to a compound or polymer containing a substituted piperidinyl group. In some embodiments, a substituted piperidinyl group may contain 1, 2, 3, 4, 5, 6, 7, 8 or more substituents, such as alkyl, alkenyl, or alkoxy groups. In some embodiments, a substituted piperidinyl group has one or two substituents at the 2- and/or 6-positions of the piperidine ring (e.g., a C ₁ -C ₂₀ alkyl or C ₁ -C ₂₀ alkenyl group). ) includes. In some embodiments, the substituted piperidinyl group is a 2,2,6,6-tetraalkylpiperidinyl group (e.g., 2,2,6,6-tetramethylpiperidinyl group). In some embodiments, the substituted piperidinyl group includes hydrogen, an alkyl group, or an alkoxy group at the 1-position of the piperidine ring. In some embodiments, sterically hindered amine light stabilizers include amine groups that act through and/or participate in regenerative free radical scavenging mechanisms.

One or more (e.g., 1, 2, 3, 4, 5 or more) substituted piperidinyl group(s) may be present in the hindered amine light stabilizer. In some embodiments, the sterically hindered amine light stabilizer is a polymer and has one or more (e.g., 1, 2, 3, 4, 5 or more) substituted piperi per repeat unit of the sterically hindered amine light stabilizer. Contains dinyl group(s). In some embodiments, the acrylic compositions of the present invention contain one or more (e.g., 1, 2, 3, 4 or more) 2,2,6,6-tetraalkylpyrrolidyl groups in a sterically hindered amine light stabilizer. A sterically hindered amine light stabilizer comprising peridinyl group(s) may be included. In some embodiments, the sterically hindered amine light stabilizer may be a polymeric or oligomeric sterically hindered amine light stabilizer, with one or more (e.g., 1, 2, 3, 4) per repeat unit of the sterically hindered amine light stabilizer. or more) of 2,2,6,6-tetraalkylpiperidinyl groups.

Examples of sterically hindered amine light stabilizers include, but are not limited to, those sold under the trade name Tinuvin® from BASF, for example Tinuvin® PA 123, Tinuvin® 371 , Tinuvin (registered trademark) 111 and/or Tinuvin (registered trademark) 622; Marketed under the trade name Chimassorb® from BASF, for example Chimassorb® 2020; and/or those sold under the trade name Cyasorb® from Cytec Industries, Inc., such as Cyasorb® UV-3529. .

secondary antioxidant

The polyester composition of the present invention contains one or more secondary antioxidants. Secondary antioxidants may be any known in the art. When selecting a secondary antioxidant, molecular weight, reactivity, and hydrolytic stability can be considered. Examples of secondary antioxidants include thiodipropionate, phosphite, and metal salts. Thiopropionates are mainly used in polyolefins and have limited use in condensation polymers. Phosphites are most typically used in thermoplastics. The structure of a typical phosphite antioxidant is presented below:

In the above formula, R is selected from C ₁ -C ₂₀ -alkyl groups.

When selecting a secondary antioxidant, molecular weight, reactivity, and hydrolytic stability must all be considered. Secondary antioxidants may also be selected from organophosphates, thioesters, or combinations thereof. In another embodiment, the secondary antioxidant is tris(nonyl phenyl)phosphite (Weston™ 399 (available from Addivant, CT, USA), tetrakis(2,4 -di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite, tris(2,4-di-tert-butylphenyl)phosphite (irgaphos( Irgafos (trade name) 168, available from BASF), bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite phosphite, and distearyl pentaerythritol diphosphite.

In one embodiment, the polyester composition of the present invention contains one or more phosphites, including an aryl phosphite or an aryl monophosphite. As used herein, the term “aryl monophosphite” refers to (1) one phosphorus atom per molecule; and (2) one or more aryloxide (which may also be referred to as phenoxide) radicals bound to phosphorus. In one embodiment, the aryl monophosphite contains a C ₁ -C ₂₀ , C ₁ -C ₁₀ , or C ₂ -C ₆ alkyl substituent on at least one of the aryloxide groups. Examples of C ₁ -C ₂₀ alkyl substituents include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and iso-butyl, tert-butyl, pentyl, hexyl, octyl, Includes nonyl and decyl. Preferred aryl groups include phenyl and naphthyl.

In one embodiment, phosphites useful in the invention include tert-butyl-substituted aryl phosphites. In another embodiment, the aryl monophosphite is triphenyl phosphite, phenyl dialkyl phosphite, alkyl diphenyl phosphite, tri(nonylphenyl)phosphite, tris-(2,4-di-t-butylphenyl) Phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite (think Irgaphos™ 38, available from BASF), 2,2,2-nitrilo[triethyltris (3,3,5,5-tetra-tert-butyl-1,1-biphenyl-diyl)phosphite (supposed to be Irgaphos(TM) 12 available from BASF). In another embodiment, the aryl monophosphite is tris-(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, and 2 , 2,2-nitrilo[triethyltris(3,3,5,5-tetra-tert-butyl-1,1-biphenyl-diyl)phosphite. In another embodiment, the aryl monophosphite useful in the invention is tris-(2,4-di-t-butylphenyl)phosphite.

In one embodiment, suitable secondary antioxidant additives are, for example, organic phosphites, such as tris(nonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2, 4-di-t-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite; or combinations comprising at least one of the antioxidants described above.

In one embodiment, the secondary antioxidant is present in an amount of about 0.01% to about 3.0%, or 0.01% to 2%, or 0.01% to 1%, or 0.10% by weight, based on the total weight of the polymer composition. % by weight to 5% by weight, or 0.10% to 4% by weight, or 0.10% to 3% by weight, or 0.10% to 2% by weight, or 0.10% to 1% by weight, or 0.25% to 1% by weight. % by weight, or in an amount of 0.25% to 0.75% by weight.

In another embodiment, the secondary antioxidant is present in the polyester composition in an amount from about 0.01% to about 2.5% by weight. In another embodiment, the secondary antioxidant is present in an amount from about 0.5% to about 2.5% by weight. In another embodiment, the secondary antioxidant is present in an amount from about 0.5% to about 2.0% by weight. In another embodiment, the secondary antioxidant is present in an amount from about 0.05% to about 0.75% by weight. In another embodiment, the secondary antioxidant is present in an amount from about 0.05% to about 0.75% by weight. In certain embodiments, the secondary antioxidant is present in an amount of from about 0.1% to about 1.0% by weight, or from about 0.2% to about 0.8% by weight, or from 0.25 to 0.75% by weight. In one embodiment, the secondary antioxidant is present in an amount of about 0.35% to about 0.65% by weight.

In certain embodiments of the invention, the weight ratio of primary to secondary antioxidants present in the polyester compositions useful in the invention may be from 5:1 to 1:5. In certain embodiments of the invention, the weight ratio of primary antioxidant to secondary antioxidant is 5:1, or 4:1, or 3:1, or 2:1, or 1:1, or 1:2, or 1. :3, or 1:4, or 1:5. In certain embodiments of the invention, the weight ratio of primary antioxidant to secondary antioxidant is 1:1, or 1:2, or 1:3, or 1:4, or 1:5. In certain embodiments of the invention, the weight ratio of primary antioxidant to secondary antioxidant is from 2:1 to 1:2, for example 2:1. In certain embodiments of the invention, the weight ratio of primary antioxidant to secondary antioxidant is 1.1:1 to 4:1, or 1.2:1 to 4:1, or 1.5:1 to 4:1, or 1.6:1 to 1.6:1. 4:1, or 1.8:1 to 4:1, or 2:1 to 4:1, or 1.1:1 to 3:1, or 1.2:1 to 3:1, or 1.5:1 to 3:1, or 1.6:1 to 3:1, or 1.8:1 to 3:1, or 2:1 to 3:1, or 1.1:1 to 2.5:1, or 1.2:1 to 2.5:1, or 1.5:1 to 2.5 :1, or 1.6:1 to 2.5:1, or 1.8:1 to 2.5:1, or 2:1 to 2.5:1.

The polyester compositions of the present invention may include one or more chain extenders. Suitable chain extenders include, but are not limited to, multifunctional (e.g., but not limited to, difunctional) isocyanates, multifunctional epoxides, such as phenoxy resins. In one embodiment, the chain extender has an epoxide dependent group. In one embodiment, the chain extending additive may be one or more styrene-acrylate copolymers with epoxide functionality. In one embodiment, the chain extending additive may be one or more copolymers of glycidyl methacrylate and styrene.

Chain extension additives include compounds such as bisanhydrides, bisoxazolines, bisepoxides, which react with -OH or -COOH end groups resulting from hydrolysis. Additionally, chain extension additives may be added during melt processing to build molecular weight through 'reactive extrusion' or 'reactive chain coupling'. Another effective type of chain extending additive is styrene-acrylate copolymers with epoxy functionality.

In certain embodiments, the chain extender is added near the end of the polymerization process or after the polymerization process. When added after the polymerization process, the chain extender can be incorporated by compounding or by addition during the conversion process (eg, injection molding or extrusion).

The amount of chain extender used may vary depending on the specific monomer composition used and the physical properties desired, but is generally from about 0.01% to about 10% by weight, or from 0.1% to about 0.1% by weight, based on the total weight of the polyester. 10% by weight, or about 0.01% to about 5% by weight, or about 0.1 to about 5% by weight, or about 0.01% to about 3% by weight, or about 0.1 to about 3% by weight, or about 0.01% by weight About 2%, or about 0.1 to about 2%, or about 0.01% to about 1%, or about 0.1 to about 1%, or about 0.01% to about 0.5%, and about 0.1% by weight. to about 0.5% by weight.

Chain extending additives may also be added during melt processing to build molecular weight through 'reactive extrusion' or 'reactive chain coupling' or any other process known in the art.

Chain extenders useful in the present invention include, but are not limited to, copolymers of glycidyl methacrylate (GMA) and alkenes, copolymers of GMA with alkenes and acrylic acid esters, copolymers of GMA with alkenes and vinyl acetates, GMA and It may include a copolymer of styrene. Suitable alkenes include ethylene, propylene, and mixtures of two or more of the foregoing. Suitable acrylic acid esters include alkyl acrylate monomers such as, but not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and combinations of the alkyl acrylate monomers described above. The acrylic acid ester, if present, may be used in an amount of 15% to 35% by weight, based on the total amount of monomers used in the copolymer, or any other range described herein. Vinyl acetate, if present, may be used in an amount of 4% to 10% by weight based on the total amount of monomers used in the copolymer.

In certain embodiments, the chain extension additive includes an acrylic acid ester comprising a monomer selected from alkyl acrylate monomers (e.g., methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and combinations thereof). In embodiments, the chain extending additive is a copolymer comprising one or more acrylic acid esters and styrene.

Illustrative examples of suitable chain extenders include ethylene-glycidyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-glycidyl meta. Crylate-alkyl acrylate copolymer, ethylene-glycidyl methacrylate-methyl acrylate copolymer, ethylene-glycidyl methacrylate-ethyl acrylate copolymer, and ethylene-glycidyl methacrylate-butyl. Contains acrylate copolymers.

Joncryl (trade name) 4368, Joncryl (trade name) 4468 (copolymer of glycidyl methacrylate and styrene), Joncryl (trade name) 4368, Joncryl (trade name) 4470, Joncryl (trade name) 4370, Joncrill (trade name) 4400, Joncrill (trade name) 4300, Joncrill (trade name) 4480, Joncrill (trade name) 4380, Joncrill (trade name) 4485, Joncrill (trade name) 4385 and mixtures thereof are sold by BASF Corporation. It is commercially available from BASF Corporation (New Jersey, USA).

In one embodiment, the chain extender can be a styrene-acrylate copolymer with glycidyl groups. In another embodiment, the chain extender may be a copolymer of glycidyl methacrylate and styrene.

In one embodiment, the polymeric chain extender has an average of at least 2 pendant epoxy groups per molecule; or three or more pendant epoxy groups per molecule; or an average of 4 or more pendant epoxy groups per molecule; or an average of 5 or more pendant epoxy groups per molecule; or an average of 6 or more pendant epoxy groups per molecule; or an average of 7 or more pendant epoxy groups per molecule; or more specifically, an average of at least 8 pendant epoxy groups per molecule; or more specifically, an average of 11 or more pendant epoxy groups per molecule; or more specifically, an average of 11 or more pendant epoxy groups; or at least 15 pendant epoxy groups per molecule; More specifically, it may have an average of 17 or more pendant epoxy groups per molecule. The lower limit on the number of pendant epoxy groups can be determined by one skilled in the art to apply to specific manufacturing conditions and/or specific end uses. In certain embodiments, the chain extender has 2 to 20 pendant epoxy groups per molecule, or 5 to 20 pendant epoxy groups per molecule, or 2 to 15 pendant epoxy groups per molecule, or 2 to 10 pendant epoxy groups per molecule. groups, or 2 to 8 pendant epoxy groups per molecule, or 3 to 20 pendant epoxy groups per molecule, or 3 to 15 pendant epoxy groups per molecule, or 5 to 15 pendant epoxy groups per molecule, or 3 per molecule. It can have from 1 to 10 pendant epoxy groups, or from 5 to 10 pendant epoxy groups per molecule, or from 3 to 8 pendant epoxy groups per molecule, or from 3 to 7 pendant epoxy groups per molecule.

In certain embodiments of the invention, the chain extender is present in an amount of 0.01% to 5%, or 0.01% to 4%, or 0.01% to 3%, based on the total weight of 100% polymer composition. %, or 0.01% to 2% by weight, or 0.01% to 1% by weight, or 0.10% to 5% by weight, or 0.10% to 4% by weight, or 0.10% to 3% by weight, or 0.10% by weight. % to 2% by weight, or 0.10% to 1.5% by weight, or 0.10% to 1% by weight, or 0.25% to 5% by weight, or 0.25% to 4% by weight, or 0.25% to 3% by weight. , or 0.25% to 2% by weight, or 0.25% to 1.5% by weight, or 0.25% to 1% by weight, or 0.25% to 0.75% by weight, or 0.50% to 5% by weight, or 0.50% by weight. in an amount of from 4% to 4% by weight, or from 0.50% to 3% by weight, or from 0.50% to 2% by weight, or from 0.50% to 1.5% by weight, or from 0.50% to 1.2% by weight, or from 0.50% to 1% by weight. (total loading) may be present in the polyester composition of the present invention. In certain embodiments, the chain extender may be present in the polymer compositions of the present invention in an amount (total loading) of 0.25% to 0.75%, or 0.30% to 0.70%, or 0.4% to 0.6% by weight. .

In certain embodiments of the invention, the chain extender is added to the polyester of the invention in an amount (total loading) of 0.01% to 1.5%, or 0.10% to 1% by weight, based on the total weight of the polyester composition. may be present in the composition.

The initial amount of chain extender used and the order of addition will vary depending on the particular chain extender selected and the specific amount of polyester used.

In one embodiment, the weight ratio of chain extender to primary antioxidant present in the polyester compositions useful in the present invention may be from 5:1 to 1:5. In certain embodiments of the invention, the weight ratio of chain extender to primary antioxidant is 5:1, or 4:1, or 3:1, or 2:1, or 1:1, or 1:2, or 1: It may be 3, or 1:4, or 1:5. In certain embodiments of the invention, the weight ratio of chain extender to primary antioxidant is 3:1 to 1:2, or 2.5 to 3:1. In certain embodiments of the invention, the weight ratio of chain extender to primary antioxidant is 1:2 or 3:1.

In certain embodiments of the invention, the weight ratio of chain extender to secondary antioxidant present in the polyester compositions useful in the invention may be from 5:1 to 1:5. In certain embodiments of the invention, the weight ratio of chain extender to secondary antioxidant is 5:1, or 4:1, or 3:1, or 2:1, or 1:1, or 1:2, or 1: It may be 3, or 1:4, or 1:5. In certain embodiments of the invention, the weight ratio of chain extender to secondary antioxidant is 3:1. In certain embodiments of the invention, the weight ratio of chain extender to secondary antioxidant is 1:1, or 1.5:1, or 1.3:1. In other embodiments, the weight ratio of chain extender to secondary antioxidant is 1:1 to 3:1, or 1:1 to 2:1.

In certain embodiments, the polyester composition comprises (1) pentaerthritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, octadecyl-3-( 3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N'-hexane-1,6-diyl-bis[3-(3,5-di-tert-butyl) -4-hydroxyphenyl)propionamide, benzenepropanoic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxyoctadecyl ester and octadecyl-3-(3,5-di-tertiary) At least one sterically hindered phenolic antioxidant comprising at least one compound selected from -butyl-4-hydroxyphenyl)-propionate (CAS No. 2082); (2) tris-(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, and 2,2,2-nitrilo[ At least one phosphite selected from triethyltris(3,3,5,5-tetra-tert-butyl-1,1-biphenyl-diyl)phosphite; and (3) one or more chain extenders that are copolymers of glycidyl methacrylate and styrene.

In certain embodiments, the polyester composition comprises at least one sterically hindered phenolic antioxidant that is pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; one or more phosphites that are tris(2,4-di-tert-butylphenyl)phosphite; and one or more chain extenders that are Joncrill™ 4468 additives.

In one embodiment of the invention, the primary antioxidant is of the sterically hindered phenol family (i.e., Irganox™ 1010, available from BASF Corporation, NJ, USA) in an amount of 0.01 to about 2.0% by weight. Included in the phosphite series (i.e., Irgaphos(TM) 168 commercially available from BASF Corporation, NJ, USA) in an amount of 0.01 to 2.0% by weight, and chains of the styrene-acrylate copolymer series In extenders (i.e., Joncryl™ 4468 available from BASF Corporation, NJ, USA) they are included in amounts of 0.01 to 2.0% by weight relative to the polyester or copolyester.

In one embodiment, the polyester composition comprises (1) one or more phenolic antioxidants in an amount of 0.01% to 2.0% by weight, (2) 0.10% to 1.0% by weight, based on the total weight of the polyester composition. % of one or more phosphites, and (3) said chain extender in an amount of 0.25% to 2.0% by weight.

In one embodiment, the polyester composition has, based on the weight of the polyester composition: (1) 0.10% to 1.5%, or 0.10% to 1.0%, or 0.50% to 1.5%, by weight; or one or more phenolic antioxidants in an amount of 0.75% to 1.25% by weight, (2) one or more antioxidants in an amount of 0.10% to 1.0%, or 0.10% to 0.75%, or 0.25% to 0.75% by weight. a phosphite, and (3) one or more chain extenders in an amount of 0.10 wt.% to 1.0 wt.%, or 0.25 wt.% to 1.0 wt.%, or 0.25 wt.% to 0.75 wt.%.

In one embodiment, the polyester composition comprises (1) one or more phenolic antioxidants in an amount of 0.75% to 1.25% by weight, (2) 0.10% to 1.0% by weight, based on the weight of the polyester composition. , or one or more phosphites in an amount of 0.25% to 0.75% by weight, and (3) one or more chain extenders in an amount of 0.10% to 1.0%, or 0.25% to 0.75% by weight.

In one embodiment, the polyester composition comprises a primary antioxidant of the sterically hindered phenol series, preferably Irganox® 1010 (available from BASF) in an amount of 0.01 to about 2.0 weight percent; A secondary antioxidant of the phosphite series, preferably Irgaphos® 168 (available from BASF) in an amount of 0.01 to 0.5% by weight, or Doverphos (registered trademark) in an amount of 0.01 to 0.5% by weight. ) 9228; and a chain extender of the styrene-acrylate copolymer series, preferably Joncryl™ 4468 (available from BASF) in an amount of 0.01 to 2.0% by weight, wherein the weight% is the weight of the polyester composition. It is based on .

In one embodiment, the present invention may use primary antioxidants of the sterically hindered phenol type, secondary antioxidants of the phosphite series, and chain extenders with epoxide functionality.

The weight percentages specified herein may also be combined with the ratios of the specified additives to each other. It may also be combined with the specific classes of additives described herein. The weight ratio of one additive to another or the weight percent of additives is calculated based on the weight of the additive relative to the total weight of the polyester composition when the additive is loaded into the composition (total loading), where all components are 100% by weight. am.

In one embodiment of the invention, the polyester composition comprises at least one rigid polyester, at least one polyester elastomer, from about 0.1 to about 2 weight percent of at least one sterically hindered phenol primary antioxidant, from about 0.01 to about 0.5% by weight. weight percent of one or more phosphite secondary antioxidants, and about 0.01 to about 2.0 weight percent of one or more styrene-acrylate copolymers, where the weight percent is based on the total weight of the polyester composition.

In one embodiment, the stabilizer composition useful in the present invention improves or maintains color, reduces loss of number average molecular weight and/or intrinsic viscosity, and/or reduces the total number of carboxyl end groups under the conditions specified herein. The number can be reduced.

This combination of primary antioxidants, secondary antioxidants and chain extenders useful in the present invention has been shown to be effective in the polyester compositions. Improved thermal oxidation and hydrolytic stability can be measured through any method known in the art, such as through the use of gel permeation chromatography and through visual color observation, colorimetry and/or spectrophotometry. Viscosity improvement can be measured using any method known in the art, such as parallel plate rheometry or intrinsic viscosity measurement. The number of carboxyl end groups can be determined through titration.

Additionally, polyester compositions useful in the present invention may also contain colorants, dyes, release agents, flame retardants, plasticizers, nucleating agents, other stabilizers (such as, but not limited to, UV stabilizers, thermal stabilizers, hydrolytic stabilizers), It may contain one or more other additives selected from fillers and impact modifiers. In embodiments, the polymer composition is 0.01 to 25%, or 0.01 to 20%, or 0.01 to 15%, or 0.01 to 10%, or 0.01 to 5% by weight of the total weight of the polyester composition. conventional additives such as colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers such as, but not limited to, UV stabilizers, thermal stabilizers and/or their reaction products, fillers and impact modifiers. It can be included. Examples of typical commercially available impact modifiers that are well known in the art and useful in the present invention include, but are not limited to, ethylene/propylene terpolymers; functionalized polyolefins, such as those containing methyl acrylate and/or glycidyl methacrylate; Includes styrenic block copolymer impact modifiers and various acrylic core/shell type impact modifiers. For example, UV additives can be incorporated into the article through addition to the bulk, through application of a hard coat, or through coextrusion of the cap layer. The residues of these additives are also considered part of the polymer composition.

Reinforcing materials may be useful in the polyester compositions of the present invention. Reinforcing materials may include, but are not limited to, carbon filaments, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers, polymeric fibers, and combinations thereof. In one embodiment, the reinforcing material is glass, such as fibrous glass filaments, mixtures of glass and talc, mixtures of glass and mica, and mixtures of glass and polymer fibers.

In certain embodiments, the polyester compositions of the present invention may be blended with any other polymers known in the art. For example, the polyester composition of the present invention may include one or more polymers selected from at least one of the following: poly(etherimide), polyphenylene oxide, poly(phenylene oxide)/polystyrene blend, polystyrene resin. , polyphenylene sulfide, polyphenylene sulfide/sulfone, poly(ester-carbonate), polycarbonate, polysulfone, polysulfone ether, and poly(ether-ketone).

In one embodiment, the polyester composition of the present invention contains no more than 50%, no more than 40%, or no more than 30%, or no more than 20% by weight of certain additional polymers other than those described in the polyester composition, such as polycarbonate; or 10% by weight or less, or 5% by weight or less; In another embodiment, 0.01 to 50% by weight, or 1 to 50% by weight, or 5 to 50% by weight, or 0.01 to 40% by weight, or 0.01 to 30% by weight, or 0.01 to 20% by weight, or 0.01 to 0.01% by weight. It may be present in an amount of 10% by weight, or 0.01 to 5% by weight.

In certain embodiments, the polyester compositions of the present invention may include one or more other polymers. In embodiments, the one or more other polymers are liquid crystalline polyesters/amides/imides, polyesteramides, polyimides, polyetherimides, polyurethanes, polyureas, polybenzimidazoles, polybenzoxazoles, polyimines, polyimides. selected from carbonates, other polyesters, other copolyesters and polyamides. In one embodiment, the polyester composition does not include polycarbonate. In one embodiment, the polyester composition does not include bisphenol polycarbonate. In one embodiment, the polyester composition does not include polybutylene terephthalate. In one embodiment, the polyester composition does not include polyarylene ether. In one embodiment, the polyester composition does not include cellulose esters.

In certain embodiments of the above polyester compositions, the one or more other polymers are present in an amount of 50% or less, or 40% or less, or 30% or less, or 20% by weight, based on the total weight of the 100% by weight polyester composition. It is present in the composition in an amount of up to % by weight, or up to 10% by weight, or up to 5% by weight. In embodiments, the one or more other polymers are present in an amount of 0.01 to 50 weight percent, or 1 to 50 weight percent, or 5 to 50 weight percent, or 0.01 to 40 weight percent, based on the total weight of the 100 weight percent polyester composition. %, or 0.01 to 30% by weight, or 0.01 to 20% by weight, or 0.01 to 10% by weight, or 0.01 to 5% by weight.

In embodiments, the polyester compositions described herein do not contain carbon nanotubes.

Effective amounts of primary antioxidants, secondary antioxidants and chain extension additives can be determined by suitability for application requirements, understanding the target properties and/or target criteria for different applications and/or thermoplastic processing conditions, and/or determining the properties selected during processing. It can be decided if it is preserved.

Method for producing polyester compositions

The polyester composition of the present invention may be prepared by any method known in the art. To prepare the polyester composition, blends of primary antioxidants, secondary antioxidants, chain extenders, rigid polyesters and polyester elastomers can be prepared directly during the polymerization process or by using typical plastic compounding and extrusion techniques. Pellets can be created by compounding using .

In one embodiment, for making a polyester composition, a mixture of (a) one or more rigid polyesters; (b) one or more polyester elastomers; (c) one or more primary antioxidants; (d) one or more secondary antioxidants; and (e) contacting one or more chain extending additives, wherein the polyester composition has a melting enthalpy of less than 3 cal/gm.

The rigid polyester, the polyester elastomer, the primary antioxidant, the secondary antioxidant and the chain extending additive are extruded from a twin screw compounding extruder, a single screw extruder, a Banbury brand mixer or a Farrell brand mixer. It can be melt compounded in a continuous mixer (trade name) to produce a homogeneous blend. In one embodiment, the rigid polyester and the polyester elastomer melt at 240°C or lower, 230°C or lower, 220°C or lower, 210°C or lower, 200°C or lower, 190°C or lower, or 180°C or lower.

In one embodiment, in an extrusion zone to produce a polyester composition, a mixture of (a) one or more rigid polyesters; (b) one or more polyester elastomers; (c) one or more primary antioxidants; (d) one or more secondary antioxidants; and (e) extruding at least one chain extending additive, wherein the polyester composition has a melt enthalpy of less than or equal to 3 cal/gm. The extrusion zone includes one or more extruders. Examples of this have been provided previously herein.

In another embodiment, (1) polymerizing (a) one or more dicarboxylic acids and one or more diols, and (b) one or more secondary antioxidants to produce a rigid polyester having a T _g greater than 60°C. step; (2) polymerizing at least one dicarboxylic acid, at least one diol, and at least one polyol to produce a polyester elastomer having a T _g of less than 0° C., and (3) combining the rigid polyester with the polyester elastomer. A method of making a polyester composition is provided, comprising contacting a polymer and one or more chain extending additives to produce a polyester composition, wherein the polyester composition has an enthalpy of melt of less than or equal to 3 cal/gm; The polymerization of steps (1) and/or (2) is carried out in the presence of one or more primary antioxidants; The polymerization of steps (1) and/or (2) is carried out in the presence of one or more secondary antioxidants.

In another embodiment of the invention, (1) polymerizing one or more dicarboxylic acids and one or more diols in the presence of (a) one or more primary antioxidants and (b) one or more secondary antioxidants, at a temperature above 60°C. producing a rigid polyester having a T _g of; (2) polymerizing at least one dicarboxylic acid, at least one diol, and at least one polyol to produce a polyester elastomer having a T _g of less than 0° C., (3) combining the rigid polyester with the polyester elastomer. and contacting with one or more chain extending additives to produce a polyester composition, wherein the polyester composition has a melt enthalpy of less than 3 cal/gm.

In another embodiment of the invention, the method comprises: (1) polymerizing one or more dicarboxylic acids and one or more diols to produce a rigid polyester having a T _g greater than 60°C; (2) polymerizing one or more dicarboxylic acids, one or more diols, and one or more polyols in the presence of (a) one or more primary antioxidants and (b) one or more secondary antioxidants to obtain a T _g of less than 0°C. producing a polyester elastomer having; and (3) contacting the rigid polyester with the polyester elastomer and one or more chain extending additives to produce a polyester composition, wherein the polyester composition has 3 It has a melting enthalpy of less than cal/gm.

The types of rigid polyesters, polyester elastomers, primary antioxidants, secondary antioxidants and chain extending additives as well as the amounts used have been previously described herein.

The polyesters and copolyesters of the present invention are readily prepared by methods well known in the art, such as those described in U.S. Pat. No. 2,012,267, the entirety of which is incorporated herein by reference. More specifically, the reaction to prepare the polyester generally proceeds at about It is carried out at a temperature of 150°C to about 300°C. The catalyst is typically used in amounts of 10 to 1000 ppm based on the total weight of reactants.

In certain embodiments, the primary antioxidant may be in the form of a masterbatch concentrate, which includes one or more rigid polyesters, a primary antioxidant, and, optionally, a secondary antioxidant.

In certain embodiments, the secondary antioxidant may be in the form of a masterbatch concentrate, which includes one or more rigid polyesters, a secondary antioxidant, and, optionally, a primary antioxidant.

In certain embodiments, the primary antioxidant may be in the form of a masterbatch concentrate, which includes one or more polyester elastomers, a primary antioxidant, and, optionally, a secondary antioxidant.

In certain embodiments, the secondary antioxidant is in the form of a masterbatch concentrate, the masterbatch concentrate comprising one or more polyester elastomers, a secondary antioxidant, and, optionally, a primary antioxidant.

The amount of primary antioxidant and/or secondary antioxidant in the masterbatch concentrate is sufficient to supply the level of antioxidant as previously described herein.

End uses of the polyester composition of the present invention

An article is provided comprising a polyester composition, wherein the polyester composition comprises: (a) one or more rigid polyesters; (b) one or more polyester elastomers; (c) one or more primary antioxidants; (d) one or more secondary antioxidants; and (e) one or more chain extending additives, wherein the composition has an enthalpy of melting of less than or equal to 3 cal/gm.

These fully compounded or manufactured pellets can be processed using conventional polymer processing methods, or concentrates of the above-described additives can be prepared and diluted using solvent-free polyesters and copolyesters and processed using conventional thermoplastic resin processing methods. Can be used to manufacture sheets, films, injection molded articles, and blow molded articles. To prepare powders useful for 3D printing applications or powder coating of metals, the compounded pellets can be subsequently milled at cryogenic temperatures and reduced in size. In another embodiment, the present invention also relates to articles of manufacture comprising any of the above-described polyester compositions.

The polyester compositions of the present invention may find utility in a number of applications. The polyesters of the present invention are suitable for use in low shear polymer melt processes such as rotational molding, powder slush molding, powder coating and 3D printing processes.

Areas that can benefit are applications at high temperature and humidity levels for extended periods of time. These include 3D printing of thermoplastic powders, additive printing and/or additive manufacturing, powder coating of metal articles, LED lighting, filtration media; Automotive hood applications, electrical and electronic devices under marine, aerospace, thermoplastic powder coating and chemical processing industries; This may include uses in surgical simulation devices, orthodontic and prosthetic devices, etc. In certain embodiments, the article of manufacture may include one or more light emitting diode (LED) assembly housings or reflectors. In embodiments, the article of manufacture includes one or more 3D powders or materials used in the manufacture of another article of manufacture. In embodiments, the article of manufacture is a molded or extruded article.

In embodiments, the article of manufacture is a fiber or filament.

In embodiments, the article of manufacture is a film or sheet.

For 3D printing applications where fast polymer flow due to rapid heating of the polymer from a laser or infrared heat source is helpful in ensuring a well-formed and fused article, lower shear melt viscosity is very useful.

In 3D printing, several processing methods are used, including high-speed sintering (HSS) and selective laser sintering (SLS). In the HSS process, an infrared (IR) heating lamp is used to heat the powdered polyester composition to produce useful objects, or in the SLS process, a CO ₂ laser is used to heat the powder. To speed up the printing process, the powder is held at very high temperatures, often just below its melting point, for up to 24 hours to minimize the heat generated by the IR lamp. Polymers maintained at such high temperatures and times, if the polymers are condensation polymers, may undergo thermal oxidative degradation and hydrolysis. This can cause molecular weight loss and discolor the polymer, making recycling and reprocessing impossible.

Additionally, in processes such as 3D printing from powder and traditional powder coating of metals, the ability to flow without forces other than gravity or surface tension to create homogeneous articles helps create useful and aesthetically pleasing articles. do.

The use of light emitting diodes (LEDs) in lighting applications has become increasingly common in recent years. LEDs have the advantage of high efficiency over traditional light sources and can be designed to operate for extremely long periods of time. LEDs therefore require materials of construction that can survive for long periods of time in these applications without deteriorating or losing their effectiveness. Compounded plastic materials are used as reflective materials in the construction of LEDs to provide control over the direction of the emitted light as well as to protect the actual diodes from damage. These compounded plastic materials can be thermoplastic or thermoset based on the requirements of the LED in this application. For example, high-power LEDs that require energy input greater than 1.0 watts typically use thermoset materials due to the heat generated during use. Lower wattage LEDs can use thermoplastic materials that can be injection molded. These injection molded materials are less expensive to process and can contain a variety of common materials. During assembly of the LED, the diode is soldered to the LEAD frame, and this soldering process requires that the thermoplastic material be dimensionally stable during the soldering process. This requires that the material be semi-crystalline with a crystalline melting point above 280°C. Additionally, because these molded thermoplastic parts reflect LED light from the diode, they can provide high reflectivity over the lifetime of the application. Low color and high color stability, measured via color measurements as described herein, before and after aging, are often used as surrogates for reflectance. In certain embodiments, these parts also have high mechanical properties because they protect the diodes from damage and survive various processing steps without breaking. By compounding various base resins and other additives, the properties of reflectance and high mechanical strength can be improved. These additives can provide enhanced “whiteness,” as in the case of titanium dioxide, and high toughness, as in the case of inorganic fillers (eg, glass fibers). Stabilizers and nucleating agents may also be added to improve stability and increase crystallization rate, respectively. Due to the high demand for thermoplastics in these applications, PCT is currently used in large quantities in thermoplastic LED applications. PCT has a crystalline melting point of 285°C and is carefully manufactured to produce a material with very low color (high reflectance). PCT can be mixed with titanium dioxide and glass fibers along with various stabilizers and additives to optimize the material's performance in this application. US Patent Application Publication No. 2007/0213458 discloses the use of PCT compounds in light emitting diode assembly housings.

During the manufacture of injection molded articles, thermoplastic resins undergo thermal degradation and shear-induced degradation. Additionally, waste materials that cannot be converted into useful components must be recycled to reduce total material costs. For this reason, compounded thermoplastics are much more stable to processing without significant loss of original performance. Additionally, the molded parts must maintain high reflectivity and high mechanical strength throughout their intended application lifetime (which can be as long as 20 years or more for LEDs). The present invention describes an optimized combination of additives that improve the process robustness of compounded PCT resins. Improvements in reflectance are measured through color and color stability using the color measurements described herein. Reprocessability is measured through intrinsic viscosity (I.V.) before and after the extrusion or processing step.

In another embodiment, the present invention also relates to articles of manufacture comprising any of the above-described polyester compositions.

Methods for forming the polyester compositions into articles of manufacture, fibers, films, molded articles, containers and sheets are well known in the art. The polyester composition can be used in manufactured articles, such as, but not limited to, fibers, filaments, films, sheets, containers, extruded and/or calendered and/or molded articles, such as, but not limited to, injection molded articles, extruded Articles, cast extruded articles, profile extruded articles, melt spun articles, thermoformed articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles and extrusion stretch blow molded articles. Useful for goods. Polyester compositions useful in the present invention include various types of films and/or sheets, including, but not limited to, extruded film(s) and/or sheet(s), calendered film(s) and/or sheet(s). ), compression molded film(s) and/or sheet(s), and solution cast film(s) and/or sheet(s). Methods for making films and/or sheets include, but are not limited to, extrusion, calendaring, compression molding, and solution casting. The polymer composition and/or polymer blend composition may be used to form fibers, films, light diffusing articles, light diffusing sheets, light reflecting articles, light reflecting sheets, light emitting diodes, 3D powders or other materials, 3D articles containing powders or other materials. It can be useful for The extruded sheet is further modified using typical manufacturing techniques such as thermoforming, cold bending, hot bending, adhesive bonding, cutting, drilling, laser cutting, etc. to create shapes useful for use as light reflectors and/or light diffusers. can do.

In one embodiment, a light reflector article comprising the polymer composition of the present invention may include one or more inorganic light reflecting additives, such as titanium dioxide, barium sulfate, calcium carbonate, or mixtures thereof.

Other end uses for which the polyester compositions of the invention may be used include, but are not limited to: (1) membrane backing (which may be film or woven or nonwoven (wetlaid or meltblown/meltspun) mats); (improved temperature, chemical and/or hydrolysis resistance may also be associated with this), (2) spun-laid using processes well known in the art (e.g., melt blowing and spin bonding processes); -laid) nonwoven web, where continuous PCT fibers are spun from pellets and laid into a nonwoven fabric in a single processing step; Dry or wet laid nonwoven webs using processes well known in the art (e.g., carding or air-laid processes), wherein the PCT fibers are first spun in one process and then spun in a second step. chopped into staple fibers using a dry-laying technique and laid into a nonwoven fabric), wherein the nonwoven web is suitable for air and liquid filtration media, especially at high temperatures (80 to 200° C.) or corrosive chemicals. It may be useful in filtration applications where exposure to the material is routine. Wet webs are a common method of producing filtration media.

Mechanical garments containing monofilaments, multifilaments, films, or sheets with improved thermal stability over conventional PCT, PCT copolymer, and additive formulations can be used in high-temperature manufacturing environments (e.g., belts used in dryer areas of paper and tissue manufacturing processes). ) can be used. Dry media may include, for example, high temperature and/or chemical resistant bag house filters and variations thereof used to capture contaminants in coal-fired power plants and various manufacturing processes.

Certain embodiments will involve using the polyester compositions of the present invention in film applications, such as film substrates with improved stability to high temperature processing and use conditions. High-temperature processes enable a variety of lead-free solders to films requiring good registration, flexibility, and/or optical clarity, either as a stand-alone or as part of a multilayer system that may include inks, coatings, and/or other features. lead free soldering) process may be included.

The abbreviation “wt” herein means “weight”. The intrinsic viscosity of the polymer (e.g., polyester) was determined in phenol/tetrachloroethane (60/40 (wt/wt)) at a concentration of 0.5 g/100 mL at 25°C.

The following examples further illustrate how the compositions of the subject matter of the invention may be prepared and evaluated and are purely illustrative of the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, parts are parts by weight, temperatures are in degrees Celsius or at room temperature, and loading levels are measured in weight percent based on the total weight of the initial polymer composition of 100 weight percent; Pressure is at or near atmospheric pressure.

By comparing data in related working examples, it has been shown that within certain loading levels, combinations of primary antioxidants, secondary antioxidants and chain extenders useful in the present invention can improve the oxidation stability, color and flow of certain polymers. can be clearly seen.

Although the invention has been described in detail with reference to the embodiments disclosed herein, it will be understood that variations and modifications may be made within the scope of the invention.

The present invention may have utility in a variety of applications. Areas that can benefit are applications at high temperature and humidity levels for extended periods of time. This includes applications for 3D printing of thermoplastic powders, powder coating of metal articles, LED lighting; Electrical and electronic devices under the hood automotive applications, marine, aerospace, thermoplastic powder coating and chemical processing industries; surgical simulation device; and orthodontic and prosthetic devices.

Method for making articles comprising polyester compositions

In one embodiment of the invention, a method of making a polyester-coated article is provided, the method comprising coating the article with a polyester composition to produce a polyester-coated article, wherein The polyester composition includes (a) one or more rigid polyesters; (b) one or more polyester elastomers; (c) one or more primary antioxidants; (d) one or more secondary antioxidants; and (e) one or more chain extending additives, wherein the composition has a melting enthalpy of less than or equal to 3 cal/gm.

In another embodiment of the present invention, a surface coating method is provided comprising the following steps:

a. Providing a polyester composition in powdered form, thereby producing a powdered polyester composition;

b. Spreading the powdered solid polyester composition on a surface;

c. heating the powdered polyester composition to form a molten polyester coating; and

d. Cooling the molten polyester coating to form a solid polyester coating.

In another embodiment, a method of coating a metal article is provided comprising the following steps:

a. Providing a polyester composition in powder form to produce a powdered polyester composition;

b. Spreading the powdered solid polyester composition on a metal surface;

c. heating the powdered polyester composition on the metal surface to form a molten polyester coating; and

d. Cooling the molten polyester coating on the metal surface to form a solid polyester coating on the metal surface.

The metal surface can be any type of household appliance, such as a dishwasher rack.

In another embodiment of the present invention, a method of making a molded article is provided, the method comprising:

1. Putting a polyester composition into a mold having a mold surface, the polyester composition comprising: (a) one or more rigid polyesters; (b) one or more polyester elastomers; (c) one or more primary antioxidants; (d) one or more secondary antioxidants; and (e) one or more chain extending additives, wherein the composition has an enthalpy of melting of less than or equal to 3 cal/gm;

2. Heating the polyester composition until melted;

3. Dispersing the molten polyester composition to cover the mold surface;

4. Solidifying the molten polyester to form a solid, molded article; and

5. Taking the molded article out of the mold

Includes.

Example

Samples for all tests were compounded on a Coperion 25 mm twin screw compounding extruder to produce pellets. The screw RPM was set to 200, and zone 1 was set to 180°C. Zones 2 to 11 were set at 250°C and the die was set at 250°C. For samples 8 and 9, the barrel temperature had to be increased to 280°C because the pellets did not melt. The extrudate came out of the two-hole die and entered a water bath for cooling and then into a pelletizer. The pellets were then injection molded into 4" x 4" x 0.125" plaques and 0.125" tensile and flex bars on a BOY 22 injection molding machine. The barrel temperature was set at 240°C, the mold was set at 70°C, the injection pressure was set at 80 bar, the cooling time was set at 25 seconds, and the ejection force was set at 125 bar.

Samples for powder coating were prepared by cryogenically grinding pellets of each formulation in an attrition mill using liquid nitrogen until a particle size of approximately 100-150 μm was achieved. This powdered material was then spray coated onto cold rolled steel panels using an electrostatic coating applicator. The panels were then heated above the melting point of each formulation to form a film on each panel.

Hot stage microscopy method:

Hot stage microscopy is a method developed to microscopically monitor visual changes in materials as they are subjected to elevated temperatures. The system was designed around an existing stereo microscope (Nikon SMZ1000). Images were captured from the microscope's objective lens using a Point Gray Research Flea3 color camera. The camera has a 1/1.8 inch CCD sensor with a pixel size of 3.69 μm and a pixel resolution of 1928×1448. The camera and microscope were coupled using a 1" CCD C-mount adapter from SPOT Imaging Solutions. A Linkam DSC 600 hot stage system was used to control heating and cooling cycles during the experiment. Additionally, a fiber-optic halogen lamp system was used for sample illumination. No sample preparation was required, and samples were placed in 5 mm aluminum DSC pans as received. Software for integrating the digital camera and hot stage system was provided by National Instruments. Instruments, NI) It was recorded using Labview 2018. It was possible to exchange serial commands with the hot stage device using the ActiveX driver provided by Linkam, the manufacturer of the hot stage. Combined with the NI Imaqdx driver, it was possible to create images with temperature and time information displayed as an overlay.

ASTM D2240 Durometer Hardness - Experimental

Test Methods:

The durometer Type D hardness method was used for testing on a test device Rex durometer model OS-I stand. Using this method, the sample is indented by an indenter on the end of the device and the load is recorded.

Sample Dimensions: Standard ASTM D 2240 type specimens will be at least 6.0 mm thick.

Relative Humidity:

Conditioned in PCL (Lab 118) for 40 hours at a temperature of 73 ± 2°F and relative humidity of 50 ± 5% according to ASTM D-618 “Standard Practice for Conditioning of Plastics for Testing.”

Instrumentation:

A Rex durometer model OS-I stand type D was used.

ASTM D256 notched izod and ASTM D4812 unnotched izod

Notched and unnotched Izod tests:

Test specimens were cut from molded flex or tension bars and loaded into a cantilever beam for impact. In the case of the notched Izod, the rod was held in place so that the energy was concentrated at the apex of the notch. The calibrated hammer was released, the mounted specimen was shaken and impacted, and the energy required to cause "fracture" was recorded along with the "type of fracture" (non-fractured, partial, hinged, and complete). .

Test Methods:

All samples were prepared and tested according to ASTM D256 A and ASTM D4812. Samples consisted of standard 2.50 ± 0.08 in × 500 ± 0.008 in, and flex or tension bars cut to widths from 0.118 to 0.500 in (typically 0.125 in) and, if notched Izod was requested, 10.16 ± 0.05 mm from bar center. A “notch was created” with a depth of . This was verified using a calibrated Mitutoyo micrometer. The notch angle was 22.5°±0.5° on both sides of the vertex, and the notch radius was cut at 0.25R±0.05.

Relative Humidity:

Conditioned for 40 hours in PCL Lab 136 at a temperature of 73 ± 2°F and relative humidity of 50 ± 5%, according to ASTM D-618 “Standard Practice for Conditioning Plastics for Testing.”

Instrumentation:

Data were collected using a cantilever beam Izod impact device and custom software from Testing Machines Incorporated (TMI). At least five specimens were tested for each sample to obtain both a “break type” average as well as an overall average.

Justice

Non-Fracture: A fracture in which more than 10% of the specimen width remains at fracture.

Partial: A fracture in which less than 10% of the specimen width remains at fracture and is self-supporting over a 90° axis.

Hinged: A fracture in which less than 10% of the specimen width remains at fracture and is unable to support itself over a 90° axis.

Complete: A break that completely separates into two pieces.

ASTM D790 Flexural Modulus

Test Methods:

The Flex method was used on the test equipment, Instron frame, using Bluehill 3 and TestMaster 2 software. Using this method, the sample can be bent at a constant rate at the center of the span, and the load is recorded as the dependent variable.

Sample Dimensions: A standard ASTM D 790 type specimen will be 3.175 mm (1/8 in) thick, 12.7 mm (0.5 in) wide, and 130 mm (5 in) long.

Relative Humidity:

According to ASTM D-618 "Standard Practice for Conditioning Plastics for Testing," samples were conditioned for 40 hours at a temperature of 73 ± 2 degrees F and a relative humidity of 50 ± 5%.

Instrumentation:

The Instron frame used Blue Hill 3 and Testmaster 2 software. Five specimens were tested for each sample to obtain an average value. The sample was tested at a span length of 2 inches at a speed of 0.05 in/min. Each sample was bent to 5.5% strain.

Glass transition temperature data

Glass transition temperature was measured using ASTM D3418-15. The sample was heated from 0°C to 280°C at a rate of 20°C/min, cooled to 0°C, and then heated again from 0°C to 280°C at a rate of 20°C/min. The glass transition temperature and heat of fusion were determined from secondary heating.

Powder application and processing:

All samples were ground using a Retsch ZM-1 centrifugal mill. The following variables can be varied to change the rate and intensity of size reduction:

RPM - 10,000 or 20,000,

Rotor - 6 or 12 teeth;

Ring sieves - available in various opening sizes.

For the first test, Sample 1 was cooled to -40°C and introduced into a grinding mill with a 1.0 mm screen and a 6-tooth rotor at 20K RPM. The resulting powder was very coarse.

Sample 1 was then combined with liquid nitrogen in a stainless steel beaker and the cooled material was fed to the mill under the same conditions as the first test. The material was easier to grind, but was still too coarse for electrostatic spraying.

The annular sieve was replaced with a sieve with 0.75 mm openings and the process was repeated. The ground material was passed through an 80 mesh (180 μm) screen and sprayed onto test panels using a fine powder. This process was repeated for the remaining thermoplastic samples.

Electrostatic application and baking:

The powder was applied to bare cold rolled steel (QD-46) and Bonderite 1000 pre-treated cold rolled steel (R-46) using a Nordson Encore electrostatic spray gun. -I) Sprayed on the test panel. The powder was easily applied to the substrate. The panel was placed in an electric convection oven at 230° C. (substrate temperature) for 15 minutes. Under these conditions, most of the material melted and flowed well. Compositions 4, 7 and 9 did not show complete melting at 230°C, so they were placed back into the oven at 250°C for 10 minutes.

Adhesion was evaluated according to ASTM 3359 crosshatch adhesion and tape pull tests.

Impact resistance was measured using a Gardner impact tester using ASTM D2794.

salt fog

The coated metal panel, scribed with an " and blister frequency were visually inspected, face rust was visually inspected according to ASTM D610, and scribe rust was visually inspected according to ASTM D1654.

tensile properties

The samples were injection molded into 3 mm thick large tensile bars (Type I) and tested according to ASTM D638.

Color, light transmittance and haze

A sample of each composition was injection molded into a 4" x 4" x 3 mm plaque, light transmittance and haze were measured according to ASTM D 1003, and color difference was measured according to ASTM D2244.

Discussion of results and observations:

The inventors have unexpectedly discovered that blends of rigid and flexible copolyesters containing an antioxidant package may be suitable for applications requiring the polymer in powder form to be processed at high temperatures and low shear. .

Important properties of powder-coated articles may include good adhesion to substrates, good impact resistance, good corrosion resistance, low temperature processing, good thermal stability and good low shear flow properties. Good adhesion is important for many cases and applications so the coating will not peel or peel off from the substrate. This may also be related to the excellent impact and corrosion resistance, because if the interfacial adhesion is damaged, corrosive liquids can penetrate under the coating and cause corrosion, resulting in low impact strength and brittle fracture without compliance and deformation during impact. Because it can cause it. Cold machining is important for saving energy and reducing cycle times during processing. Good thermal stability is important because the material can exist at elevated temperatures close to its melting point for several hours, or at highly elevated temperatures, allowing it to flow from the powder to a "liquid" state and coalesce to form a continuous film. am. This can be achieved by incorporating a powerful antioxidant system to prevent thermal oxidative degradation and molecular weight loss.

The present invention solves many of the problems described above, which can be illustrated by the examples below. Table 2 below contains data supporting the following observations.

Antioxidant systems were incorporated in Examples 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11. The importance of this will appear in other tests.

Excellent melting or flow is illustrated in Examples 1, 2, 3, 6, 7, 9, 10, and 11 because, in hot stage melt tests, they melt and flow below 240°C. This shows that the composition can melt, flow, and coalesce at reasonably low thermoplastic processing temperatures. Examples 4 and 5 did not flow well below 240°C, but still coated test panels. It should be noted that Example 8 could not be processed at all and test panels could not be made with this composition.

The excellent corrosion resistance after 500 hours of salt fog testing is illustrated by examples (1, 2, 3, 6, 10, 11) which show blister sizes greater than 6 and scribe rust values greater than 6. This shows that the material has a certain degree of interfacial adhesion to the substrate.

Excellent impact resistance is exemplified by Examples 2, 3, 5, 6, 10, and 11, with an impact resistance of 160 ft·lb as measured using the falling dart test. The importance of the antioxidant package is that Example 1 has excellent corrosion resistance (which shows some adhesion, but lacks thermal stability caused by the material not adhering to the metal panel, and fracture due to polymer decomposition). It is confirmed by

When combined with a heat of fusion criterion of 3 cal/gm or less, only Examples 2, 3, 6, 10 and 11 including the antioxidant package have the combination of excellent low shear melt flow, good corrosion resistance and good impact resistance. Excellent corrosion resistance and excellent impact resistance indicate excellent interfacial adhesion.

What is unique is that the hard part of the composition is independent of the polymer structure and chemistry, as long as the end properties of excellent low shear melt flow, good corrosion resistance and good impact resistance are achieved, and the composition has a heat of fusion of less than 3 cal/gm. It can be a feature. This is unexpected and original.

Tests for the above formulation can be found below.

Claims (20)

(a) one or more rigid polyesters;
(b) one or more polyester elastomers;
(c) one or more primary antioxidants;
(d) one or more secondary antioxidants; and
(e) one or more chain extension additives
A polyester composition comprising a melt enthalpy of 3 cal/gm or less. According to paragraph 1,
A polyester composition, wherein the polyester composition melts below 240°C. According to paragraph 1,
A polyester composition, wherein after 500 hours of salt fog testing in accordance with ASTM B117, the polyester composition exhibits a blister size of 6 or greater as determined in accordance with ASTM D714. According to paragraph 3,
A polyester composition, wherein the polyester composition exhibits a scribe rust value of at least 6 as determined by ASTM D1654. According to paragraph 1,
A polyester composition, wherein the polyester composition, when applied to a metal panel, has an impact resistance of at least 160 ft·lb as determined by ASTM D2794. According to paragraph 1,
A polyester composition, wherein the rigid polyester has a T _g greater than 60°C. According to paragraph 1,
A polyester composition, wherein the rigid polyester has a flexural modulus of greater than 1,000 Mpa as measured by ASTM D790. According to paragraph 1,
The rigid polyester has an intrinsic viscosity ranging from 0.5 to 1 dL/g, as measured in phenol/tetrachloroethane (60/40 (wt/wt)) at a concentration of 0.5 g/100 mL at 25°C, according to ASTM D4603. A polyester composition having (inherent viscosity). According to paragraph 1,
A polyester composition, wherein the polyester elastomer has a T _g of 50° C. or less. According to paragraph 1,
A polyester composition, wherein the polyester elastomer has a flexural modulus of less than 1000 Mpa as measured by ASTM D790. According to paragraph 1,
The polyester elastomer is hexahydrophthalic anhydride (HHPA), tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid, 2,3-Nobonadicarboxylic acid, 2,3-Nobonadicarboxylic acid anhydride; cyclohexane dicarboxylic acid (CHDA), including 1,2-, 1,3-, and 1,4-isomers; dimethylcyclohexane (DMCD), including 1,2-, 1,3-, and 1,4-isomers; A polyester composition comprising one or more alicyclic diacid moieties selected from the group consisting of and mixtures thereof. According to paragraph 1,
The polyester elastomer includes adipic acid, maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, dodecanedioic acid, succinic acid, succinic anhydride, and glutaric acid. , a polyester composition comprising one or more acyclic aliphatic diacid moieties selected from the group consisting of sebacic acid, azelaic acid, and mixtures thereof. According to paragraph 1,
The polyester elastomer is 2,2,4,4-tetraalkylcyclobutane-1,3-diol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,2 -Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, hydroxypivalyl hydroxypivalate, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butane Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4,4-tetramethyl-1,6-hexanediol, 1,10- One or more di-alcohol components selected from the group consisting of decanediol, 1,4-benzenedimethanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol A polyester composition comprising a moiety. According to paragraph 1,
wherein the polyester elastomer comprises one or more polyol moieties;
A polyester composition, wherein the polyol is selected from the group consisting of polytetramethylene ether glycol (PTMG), polyethylene glycol, polypropylene glycol, any other polyether polyol, and mixtures thereof. According to paragraph 1,
The polyester elastomer,
a. residues of cyclohexane dicarboxylic acid (CHDA) and dimethylcyclohexane (DMCD);
b. cyclohexane dimethanol (CHDM) moiety,
c. a polytetramethylene ether glycol (PTMG) moiety, and
d. Trimellitic anhydride (TMA) moiety
A polyester composition comprising. According to paragraph 1,
A polyester composition according to claim 1, wherein the primary antioxidant is one or more hindered phenols and/or one or more hindered amines. According to paragraph 1,
A polyester composition, wherein the secondary antioxidant is selected from the group consisting of thiodipropionate, phosphite and metal salt. According to paragraph 1,
A polyester composition, wherein the chain extender is at least one chain extender selected from the group consisting of polyfunctional isocyanates and/or polyfunctional epoxides. According to paragraph 1,
The polyester composition,
(1) Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, octadecyl-3-(3,5-di-t-butyl-4 -Hydroxyphenyl)propionate, N,N'-hexane-1,6-diyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide, benzenepropane Acids 3,5-bis(1,1-dimethylethyl)-4-hydroxyoctadecyl ester and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propio one or more sterically hindered phenolic antioxidants, including one or more compounds selected from Nate (CAS No. 2082);
(2) tris-(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, and 2,2,2-nitrilo[ At least one phosphite selected from triethyltris(3,3,5,5-tetra-tert-butyl-1,1-biphenyl-diyl)phosphite; and
(3) one or more chain extenders that are copolymers of glycidyl methacrylate and styrene.
A polyester composition comprising. According to paragraph 1,
The polyester composition comprises at least one rigid polyester, at least one polyester elastomer, from about 0.1% to about 2% by weight of one or more sterically hindered phenol primary antioxidants, from about 0.01% to about 0.5% by weight of one or more A polyester composition comprising a phosphite secondary antioxidant, and about 0.01% to about 2.0% by weight of one or more styrene-acrylate copolymers, wherein the weight percent is based on the total weight of the polyester composition. .